JP2010234361A - Electric deionized water production apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electric deionized water production apparatus which has an ion exchanger having high strength, can reduce a pressure loss during water passage, and further accelerates the movement of adsorbed ionic impurities to facilitate the removal of adsorbed ions. <P>SOLUTION: In the electric deionized water production apparatus where a direct-current electric field is applied to a deionizing chamber filled with the ion exchanger so that ions to be removed migrate in the direction identical or reverse to the water flowing direction in the ion exchanger, the ion exchanger is a mixture of a monolithic organic porous ion exchanger and a granular ion exchange resin, wherein the monolithic organic porous ion exchanger is a continuous macropore structure where cellular macropores overlap each other and the overlapped parts form openings having an average diameter of 30-300 μm in a water-wet state, has a total pore volume of 0.5-5 ml/g, has an ion exchange capacity of 0.4-5 mg equivalent/ml in a water-wet state, and, in an SEM image of the cut surface of the continuous macropore structure (in a dry state), has an skeleton area, appearing in the cut surface, of 25-50% of the image area. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to the production of electric deionized water used in various industries such as semiconductor manufacturing industry, pharmaceutical industry, food industry, power plant, laboratory, etc. using deionized water, or the production of sugar liquid, juice, wine, etc. It relates to the device.

  As a method for producing deionized water, there is conventionally known a method for deionizing granular ion exchange resin (hereinafter also simply referred to as “ion exchange resin”) through treated water. In this method, ion exchange resin is used. When the ion exchange capacity of the product decreases, it is necessary to regenerate with a chemical. To eliminate such disadvantages in processing operation, there is a method for producing deionized water by an electrical deionization method that does not require any chemical regeneration. Established and put into practical use.

  Japanese Patent Laid-Open No. 2006-15260 discloses that a DC electric field is applied to a deionization chamber filled with an ion exchanger so that ions to be eliminated migrate in the same direction or in the opposite direction to the direction of water flow in the ion exchanger. In the electric deionized water production apparatus that removes ionic impurities adsorbed on the ion exchanger out of the system, the ion exchanger is composed of a monolithic organic porous ion exchanger and a granular ion exchange resin. A monolithic organic porous ion exchanger having an open-cell structure with macropores connected to each other and mesopores having an average diameter of 1-1000 μm in the walls of the macropores, and a total pore volume of 1 ml Disclosed is an electric deionized water production apparatus in which the ion exchange groups are uniformly distributed and the ion exchange capacity is 0.5 mg equivalent / g or more of a dry porous body. It has been. Further, details of a method for producing a monolithic organic porous ion exchanger used in this electric deionized water production apparatus are disclosed in JP-A-2002-306976.

  According to the electric deionized water production apparatus disclosed in Japanese Patent Application Laid-Open No. 2006-15260, the monolith is used as part of the ion exchanger filled in the deion exchange chamber. Can be buffered by the physical stretchability of the monolith, and the filling state in the deionization chamber can be kept uniform. In addition, since it can prevent swelling and shrinkage due to ion exchange reaction and poor contact with ion exchange membrane, simplified deion exchange chamber structure with wide space that could not be achieved with a single ion exchange resin Can reduce the material cost, processing cost, and assembly cost. In addition, compared to ion exchange resins, monoliths have a faster ion movement speed and shorter ion exchanger lengths, so monoliths placed near the treated water inlet facilitate the discharge of ions and treat high-ion concentration water. The monolith arranged in the vicinity of the treated water outlet can suppress the leakage of a trace amount of ions in a dilute concentration region and obtain high-purity treated water. Also, by placing a monolith near the treated water inlet of the deionization chamber, the removal rate of hardness components such as calcium is improved in the decation chamber, and anions such as carbonic acid and silica are eliminated in the deionization chamber. Increases speed.

JP 2006-15260 A JP 2002-306976 A

  However, the organic porous ion exchangers described in JP-A-2006-15260 and JP-A-2002-306976 have a common monolithic opening (mesopore) of 1 to 1,000 μm, For monoliths with a small pore volume of 5 ml / g or less in pore volume, it is necessary to reduce the amount of water droplets in the water-in-oil emulsion, so the common aperture is small, and the average diameter of the aperture is substantially 20 μm or more. Cannot be manufactured. For this reason, there existed a problem that the pressure loss at the time of water flow was large. In addition, when the average diameter of the openings is around 20 μm, the total pore volume also increases accordingly, so that the ion exchange capacity per volume decreases, and thus the quality of treated water and the power consumption increase. There was a problem.

  Therefore, the object of the present invention is to maintain the advantages of the mixed ion exchanger of the monolith and the granular ion exchange resin filled in the horizontal desalting chamber of JP-A-2006-15260, while the strength of the ion exchanger is high, An object of the present invention is to provide an electric deionized water production apparatus that can reduce pressure loss during water flow, has good treated water quality, and has low power consumption.

  Under such circumstances, the present inventors have conducted intensive studies, and as a result, obtained a monolithic organic porous material (intermediate) having a relatively large pore volume obtained by the method described in JP-A-2002-306976. In the presence, if the vinyl monomer and the crosslinking agent are allowed to stand and polymerize in a specific organic solvent, a thick monolith having a larger skeleton than the skeleton of the intermediate organic porous material can be obtained. When an ion exchange group is introduced into a thick monolith, the swelling is large due to the thick bone, and therefore the opening can be further increased. When used as a part of a mixed ion exchanger of an electric deionized water production apparatus, the ion exchanger can be used to accelerate the movement of adsorbed ionic impurities and remove adsorbed ions. It was found that the strength of the ion exchanger was high, the pressure loss during water flow could be reduced, the quality of the treated water was good and the power consumption was small, and the present invention was completed. .

  In addition, as a result of intensive studies, the present inventors have found that a monolith-like organic porous material (intermediate) having a large pore volume obtained by the method described in JP-A-2002-306976 has a fragrance. Group vinyl monomer and cross-linking agent are allowed to stand in a specific organic solvent to form a three-dimensionally continuous aromatic vinyl polymer skeleton and three-dimensionally continuous pores between the skeleton phases. A monolith with a co-continuous structure intertwined with each other, this monolith with a co-continuous structure has a high continuity of pores, is not biased in size, and has a low pressure loss during fluid permeation, Since the skeleton of this co-continuous structure is thick, if an ion exchange group is introduced, a monolithic organic porous ion exchanger having a large ion exchange capacity per volume can be obtained, and the monolithic organic porous ion exchanger (hereinafter, referred to as “monolithic organic porous ion exchanger”). "Second The monolith ion exchanger ") can be used as a part of the mixed ion exchanger of the electric deionized water production apparatus to accelerate the movement of the adsorbed ionic impurities in the same manner as the first monolith ion exchanger. It has been found that the adsorption ion can be easily removed, the ion exchanger has high strength, the pressure loss during water flow can be reduced, the quality of the treated water is good, and the power consumption is low. It came to be completed.

  That is, the present invention applies a DC electric field to a deionization chamber filled with an ion exchanger so that ions to be excluded migrate in the same direction or in the opposite direction to the direction of water flow in the ion exchanger. In the electric deionized water production apparatus for removing ionic impurities adsorbed on the ion exchanger out of the system, the ion exchanger is a mixture of a monolithic organic porous ion exchanger and a granular ion exchange resin. The monolithic organic porous ion exchanger is a continuous macropore structure in which bubble-shaped macropores overlap each other, and this overlapping portion is an opening having an average diameter of 30 to 300 μm in a wet state of water. 5 to 5 ml / g, ion exchange capacity per volume in a wet state of water of 0.4 to 5 mg equivalent / ml, and ion exchange groups are uniformly distributed in the porous ion exchanger And in the SEM image of the cut surface of this continuous macropore structure (dry body), the skeleton part area which appears in a cross section is 25 to 50% in an image field, The electric deionized water manufacturing device characterized by the above-mentioned is provided. Is.

  In the present invention, a DC electric field is applied to a deionization chamber filled with an ion exchanger so that ions to be excluded migrate in the same direction or in the opposite direction with respect to the water flow direction in the ion exchanger. In the electric deionized water production apparatus for removing ionic impurities adsorbed on the ion exchanger out of the system, the ion exchanger is a mixture of a monolithic organic porous ion exchanger and a granular ion exchange resin. The monolithic organic porous ion exchanger has a thickness of 1 consisting of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit among all the structural units into which ion exchange groups are introduced. A co-continuous structure comprising a three-dimensionally continuous skeleton of ˜60 μm and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, and the total pore volume is 0.5˜ 5ml / g, water wet An ion-exchange capacity per volume in a state of 0.3 to 5 mg equivalent / ml, and the ion-exchange groups are uniformly distributed in the porous ion exchanger. Is to provide.

The present invention also includes a deanion chamber partitioned by an anion exchange membrane on one side and an ion exchange membrane on the other side, an anode disposed outside the anion exchange membrane on the one side, and the other side A cathode disposed outside the ion exchange membrane, supplying water to be treated from the vicinity of the anion exchange membrane on one side in the deanion ion chamber, and ions on the other side in the deanion ion chamber An anion cell for obtaining the first treated water from the vicinity of the exchange membrane;
A decation chamber partitioned by a cation exchange membrane on one side and an ion exchange membrane on the other side; a cathode disposed outside the cation exchange membrane on the one side; and an outer side of the ion exchange membrane on the other side The first treated water of the anion cell is supplied from the vicinity of one cation exchange membrane in the decation chamber, and the other ion exchange in the decation chamber is provided. The electric deionized water production apparatus includes a cation cell that obtains second treated water from the vicinity of the membrane.

The present invention also provides a decation chamber partitioned by a cation exchange membrane on one side and an ion exchange membrane on the other side, a cathode disposed outside the cation exchange membrane on the one side, and the other side Having an anode disposed outside the ion exchange membrane, supplying water to be treated from the vicinity of one cation exchange membrane in the decation chamber, and performing ion exchange on the other side in the decation chamber A cation cell for obtaining the first treated water from the vicinity of the membrane;
A deanion chamber partitioned by an anion exchange membrane on one side and an ion exchange membrane on the other side, an anode disposed outside the anion exchange membrane on the one side, and an outer side of the ion exchange membrane on the other side The first treated water of the cation cell is supplied from the vicinity of the anion exchange membrane on one side in the deanion ion chamber, and the ion exchange on the other side in the deanion ion chamber is provided. The electric deionized water production apparatus includes an anion cell that obtains second treated water from the vicinity of the membrane.

  In the present invention, the ion exchanger filled on the cathode side of the cation cell is a monolithic organic porous cation exchanger, or the ion exchanger filled on the anode side is a monolithic organic porous material. An anion exchanger, the ion exchanger filled on the anode side of the anion cell is a monolithic organic porous anion exchanger, or the ion exchanger filled on the cathode side is a monolith It is an organic porous cation exchanger, and provides the electric deionized water production apparatus.

  In addition, the present invention provides a detachment method in which an intermediate ion exchange membrane is provided between an anion exchange membrane on one side and a cation exchange membrane on the other side, and is partitioned by the anion exchange membrane on the one side and the intermediate ion exchange membrane. A decation chamber partitioned by the anion chamber, the cation exchange membrane on the other side and the intermediate ion exchange membrane; an anode outside the anion exchange membrane on the one side; and a cation on the other side A deionization cell in which a cathode is disposed outside an exchange membrane, wherein water to be treated is supplied from the vicinity of the other cation exchange membrane in the decation chamber and intermediate ions in the decation chamber First treated water is obtained from the vicinity of the exchange membrane, and the first treated water is supplied from the vicinity of the anion exchange membrane on one side of the deanion chamber, and from the vicinity of the intermediate ion exchange membrane in the deanion chamber. The electric deionized water production apparatus is characterized in that the second treated water is obtained.

  In addition, the present invention provides a desorption method in which an intermediate ion exchange membrane is provided between a cation exchange membrane on one side and an anion exchange membrane on the other side, and is partitioned by the cation exchange membrane on the one side and the intermediate ion exchange membrane. A deionization chamber defined by a cation chamber, the other side anion exchange membrane and the intermediate ion exchange membrane; a cathode outside the one side cation exchange membrane; and an anion on the other side A deionization cell in which an anode is disposed outside an exchange membrane, wherein water to be treated is supplied from the vicinity of the anion exchange membrane on the other side in the deionization chamber, and intermediate ions in the deionization chamber First treated water is obtained from the vicinity of the exchange membrane, and the first treated water is supplied from the vicinity of one cation exchange membrane in the decation chamber, and from the vicinity of the intermediate ion exchange membrane in the decation chamber. The electric deionized water production apparatus is characterized in that the second treated water is obtained.

  In the present invention, the ion exchanger filled on the cathode side of the decation chamber is a monolithic organic porous cation exchanger, or ions filled on the anode side of the deion chamber. It is an object of the present invention to provide the electric deionized water production apparatus, wherein the exchanger is a monolithic organic porous anion exchanger.

  The present invention also includes a deionization chamber partitioned by an anion exchange membrane on one side and a cation exchange membrane on the other side, an anode disposed outside the anion exchange membrane on the one side, and the other side And having a cathode disposed outside the cation exchange membrane, and filling the monolithic organic porous anion exchanger on the anode side of the deionization chamber, or monolithic organic on the cathode side of the deionization chamber In a deionization cell filled with a porous cation exchanger, water to be treated is supplied from the vicinity of the anion exchange membrane on one side in the deionization chamber, and in the vicinity of the other cation exchange membrane in the deionization chamber From the vicinity of the cation exchange membrane on the other side in the deionization chamber to obtain treated water from the vicinity of the anion exchange membrane on the one side in the deionization chamber The electric deionized water production apparatus is provided.

  According to the present invention, the strength of the ion exchanger is high while maintaining the advantages of the mixed ion exchanger of the monolith and the granular ion exchange resin filled in the horizontal desalting chamber of Japanese Patent Application Laid-Open No. 2006-15260. The pressure loss at the time can be reduced, the quality of treated water is good, and the power consumption is small. That is, compared to the monolith described in Japanese Patent Application Laid-Open No. 2006-15260, since the ion moving speed is high and the ion exchanger length is short, the monolith arranged near the treated water inlet promotes the discharge of ions and increases the The monolith which enables treatment of concentrated water and is disposed in the vicinity of the treated water outlet can suppress the leakage of a trace amount of ions in a dilute concentration region and obtain high-purity treated water.

It is a SEM image of the monolith in the 1st monolith ion exchanger. It is an EPMA image which showed the distribution state of the sulfur atom in the surface of the monolith of FIG. 2 is an EPMA image showing a distribution state of sulfur atoms in the cross-section (thickness) direction of the monolith of FIG. It is a figure which shows the correlation of the differential pressure | voltage coefficient of the reference examples 1-11 and reference examples 20-23, and the ion exchange capacity per volume. It is a manual transfer of the skeleton part that appears as a cross section of the SEM image of FIG. It is the figure which showed typically the co-continuous structure of the 2nd monolith ion exchanger. It is a SEM image of the monolith intermediate in a bicontinuous structure. It is a SEM image of the monolith cation exchanger which has a bicontinuous structure. It is the EPMA image which showed the distribution state of the sulfur atom in the surface of the monolith cation exchanger which has a bicontinuous structure. It is the EPMA image which showed the distribution state of the sulfur atom in the cross section (thickness) direction of the monolith cation exchanger which has a bicontinuous structure. It is a SEM image of the other monolith cation exchanger which has a bicontinuous structure. It is the SEM photograph of the organic porous body of the former (Unexamined-Japanese-Patent No. 2002-306976). It is a figure explaining the swelling and shrinkage | contraction of a monolith-ion exchange resin mixture. It is a schematic diagram which shows the structure of the electrical deionized water manufacturing apparatus of the 1st Example of this invention. It is a schematic diagram which shows the structure of the electrical deionized water manufacturing apparatus of the 2nd Example of this invention. It is a schematic diagram which shows the structure of the electrical deionized water manufacturing apparatus of the 3rd Embodiment of this invention. It is a schematic diagram of the electric decation water production apparatus used in the Example.

  The basic structure of the electric deionized water production apparatus of the present invention is to form a deionization chamber by filling a deionization chamber partitioned by ion exchange membranes on both sides with a mixture of a monolith and an ion exchange resin. An electrode for applying a DC electric field is arranged outside the membrane, and the application of the DC electric field is performed so that ions to be excluded migrate in the same direction or in the opposite direction to the direction of water flow in the ion exchanger. It is. The term “migrate in the same or reverse direction” means to include cases where it migrates in both the same and reverse directions. In the present invention, the direction of water flow in the mixed ion exchanger refers to the direction of water flow in the substantially central portion of the mixed ion exchanger. For example, as shown in FIG. 14, the treated water inlet and the treated water outlet are substantially diagonal in a side view, and the flow in the mixed ion exchanger is not unidirectional, i.e., not in the horizontal direction in the figure. The water flow direction in the majority of the mixed ion exchanger is generally the left-right direction, and includes such a water flow mode. In addition, although it is not necessary to arrange | position a to-be-processed water introduction distribution part and a treated water collection part separately in this mixed ion exchanger, you may install.

  The monolithic organic porous ion exchanger used in the present invention is a first monolith ion exchanger or a second monolith ion exchanger. In the present specification, “monolithic organic porous body” is simply “monolith”, “monolithic organic porous ion exchanger” is simply “monolith ion exchanger”, and “monolithic organic porous intermediate”. Is also simply referred to as “monolith intermediate”.

<Description of the first monolith ion exchanger>
The first monolith ion exchanger is obtained by introducing an ion exchange group into a monolith. Bubble-shaped macropores overlap each other, and this overlapping portion is in a water-filled state with an average diameter of 30 to 300 μm, preferably 30. It is a continuous macropore structure having openings (mesopores) of ˜200 μm, particularly 35 to 150 μm. The average diameter of the opening of the monolith ion exchanger is larger than the average diameter of the opening of the monolith because the entire monolith swells when an ion exchange group is introduced into the monolith. If the average diameter of the openings is less than 30 μm, the pressure loss at the time of water flow is increased, which is not preferable. If the average diameter of the openings is too large, contact between the fluid and the monolith ion exchanger becomes insufficient. As a result, the ion exchange characteristics deteriorate, which is not preferable. In the present invention, the average diameter of the opening of the monolith intermediate in the dry state, the average diameter of the opening of the monolith in the dry state, and the average diameter of the opening of the monolith ion exchanger in the dry state are values measured by a mercury intrusion method. It is. Moreover, the average diameter of the opening of the monolith ion exchanger in the water state is a value calculated by multiplying the average diameter of the opening of the monolith ion exchanger in the dry state by the swelling rate. Specifically, the diameter of the monolith ion exchanger in the water state is x1 (mm), the monolith ion exchanger in the water state is dried, and the diameter of the resulting monolith ion exchanger in the dry state is y1 ( mm), and when the average diameter of the opening when the dried monolith ion exchanger was measured by the mercury intrusion method was z1 (μm), the average diameter of the opening of the monolithic ion exchanger in the water state ( [mu] m) is calculated by the following formula "average diameter (μm) = z1 * (x1 / y1) of the opening of the monolithic ion exchanger in the water state". In addition, the average diameter of the opening of the dried monolith before introduction of the ion exchange group and the swelling ratio of the water-borne monolith ion exchanger with respect to the dried monolith when the ion exchange group is introduced into the dried monolith are known. In this case, the average diameter of the water state of the pores of the monolith ion exchanger can also be calculated by multiplying the average diameter of the opening of the monolith in the dry state by the swelling rate.

  In the first monolith ion exchanger, in the SEM image of the cut surface of the continuous macropore structure, the skeleton part area appearing in the cross section is 25 to 50%, preferably 25 to 45% in the image region. If the area of the skeleton part appearing in the cross section is less than 25% in the image region, it becomes a thin skeleton, which is not preferable because the ion exchange capacity per volume decreases, and if it exceeds 50%, the skeleton becomes too thick, Since the uniformity of ion exchange characteristics is lost, it is not preferable. In addition, the monolith described in JP-A-2002-346392 has a limit to the blending ratio in order to ensure a common opening even if the blending ratio of the oil phase part to water is actually increased to make the skeleton portion thick. Yes, the maximum value of the skeleton area appearing in the cross section cannot exceed 25% in the image region.

  The conditions for obtaining the SEM image may be any conditions as long as the skeleton part that appears in the cross section of the cut surface appears clearly. For example, the magnification is 100 to 600, and the photographic area is about 150 mm × 100 mm. SEM observation is preferably performed on three or more images, preferably five or more images, taken at arbitrary locations on an arbitrary cut surface of the monolith excluding subjectivity and at different locations. The monolith to be cut is in a dry state for use in an electron microscope. The skeleton part of the cut surface in the SEM image will be described with reference to FIGS. FIG. 5 is a transcribed skeleton that appears as a cross section of the SEM photograph of FIG. 1 and 5, what is generally indeterminate in shape and appears in cross section is the “skeleton part (reference numeral 52)” of the present invention, and the circular hole shown in FIG. 1 is an opening (mesopore). A relatively large curvature or curved surface is a macropore (reference numeral 53 in FIG. 5). The skeleton part area shown in the cross section of FIG. 5 is 28% in the rectangular photographic region 51. Thus, the skeleton can be clearly determined.

  In the SEM photograph, the method for measuring the area of the skeletal part appearing in the cross section of the cut surface is not particularly limited, and after specifying the skeletal part by performing known computer processing or the like, calculation by automatic calculation or manual calculation by a computer or the like A method is mentioned. The manual calculation includes a method in which an indefinite shape is replaced with an aggregate such as a quadrangle, a triangle, a circle, or a trapezoid, and the areas are obtained by stacking them.

  The first monolith ion exchanger has a total pore volume of 0.5 to 5 ml / g, preferably 0.8 to 4 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss during water passage is increased, which is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the ion exchange capacity per volume decreases, which is not preferable. Since the monolith of the present invention has an average diameter and total pore volume of the openings in the above ranges and is a thick skeleton, it is used as a part of a mixed ion exchanger of an electric deionized water production apparatus. The strength is high, the water flow differential pressure is small, and the conductivity and the quality of treated water are improved. In the present invention, the total pore volume of the monolith (monolith intermediate, monolith, monolith ion exchanger) is a value measured by a mercury intrusion method. In addition, the total pore volume of the monolith (monolith intermediate, monolith, monolith ion exchanger) is the same both in the dry state and in the water state.

  In addition, the pressure loss at the time of making water permeate | transmit the 1st monolith ion exchanger is the pressure loss at the time of letting water flow through the column filled with 1 m of the porous body at a water flow rate (LV) of 1 m / h (hereinafter referred to as “pressure loss”). , “Differential pressure coefficient”), it is preferably in the range of 0.001 to 0.1 MPa / m · LV, more preferably 0.001 to 0.05 MPa / m · LV. If the permeation rate and the total pore volume are within this range, when this is used as part of the mixed ion exchanger of an electrical deionized water production device, pressure loss during water flow is suppressed, and conductivity and treatment are reduced. It is preferable because it has sufficient mechanical strength to improve water quality.

  The first monolith ion exchanger has an ion exchange capacity of 0.4 to 5 mg equivalent / ml per volume in a water-wet state. In the conventional monolithic organic porous ion exchanger having a continuous macropore structure different from the present invention as described in JP-A-2003-334560, in order to achieve a low pressure loss that is practically required, When the opening diameter is increased, the total pore volume is increased accordingly, so that the ion exchange capacity per volume is decreased, and the total pore volume is decreased to increase the exchange capacity per volume. In addition, since the opening diameter is reduced, the pressure loss increases. On the other hand, the monolith ion exchanger of the present invention can further increase the aperture diameter and thicken the skeleton of the continuous macropore structure (thicken the skeleton wall), so that the pressure loss during permeation can be reduced. Desalination performance can be dramatically increased while keeping it low. If the ion exchange capacity per volume is less than 0.4 mg equivalent / ml, the desalting performance is lowered, which is not preferable. The ion exchange capacity per weight of the monolith ion exchanger of the present invention is not particularly limited. However, since the ion exchange groups are uniformly introduced to the surface of the porous body and the inside of the skeleton, 3 to 5 mg equivalent / g It is. The ion exchange capacity of a porous body in which ion exchange groups are introduced only on the surface cannot be determined unconditionally depending on the type of the porous body or ion exchange groups, but is at most 500 μg equivalent / g.

  In the first monolith ion exchanger, the material constituting the skeleton of the continuous macropore structure is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 50 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all structural units constituting the polymer material. It is preferable. If the cross-linking structural unit is less than 0.3 mol%, it is not preferable because the mechanical strength is insufficient. On the other hand, if it exceeds 50 mol%, embrittlement of the porous body proceeds and flexibility is lost. In particular, in the case of an ion exchanger, the amount of ion exchange groups introduced is decreased, which is not preferable. The type of the polymer material is not particularly limited, and examples thereof include aromatic vinyl polymers such as polystyrene, poly (α-methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, and polyvinyl naphthalene; polyolefins such as polyethylene and polypropylene; Poly (halogenated polyolefin) such as vinyl chloride and polytetrafluoroethylene; Nitrile-based polymer such as polyacrylonitrile; Cross-linking weight of (meth) acrylic polymer such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate Coalescence is mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, the cross-linking weight of the aromatic vinyl polymer is high due to the ease of forming a continuous macropore structure, the ease of introducing ion-exchange groups and the high mechanical strength, and the high stability to acids and alkalis. A styrene-divinylbenzene copolymer and a vinylbenzyl chloride-divinylbenzene copolymer are particularly preferable materials.

  Examples of the ion exchange group of the first monolith ion exchanger include cation exchange groups such as a sulfonic acid group, a carboxylic acid group, an iminodiacetic acid group, a phosphoric acid group, and a phosphoric acid ester group; a quaternary ammonium group and a tertiary amino group And anion exchange groups such as secondary amino group, primary amino group, polyethyleneimine group, tertiary sulfonium group and phosphonium group.

  In the first monolith ion exchanger, the introduced ion exchange groups are uniformly distributed not only on the surface of the porous body but also within the skeleton of the porous body. If the distribution of the ion exchange groups is not uniform, the movement of ions in the porous ion exchanger becomes uneven, which is not preferable because rapid removal of the adsorbed ions is hindered. Here, “ion exchange groups are uniformly distributed” means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton in the order of at least μm. The distribution of ion exchange groups can be confirmed relatively easily by using EPMA or the like. In addition, if the ion exchange groups are uniformly distributed not only on the surface of the monolith but also within the skeleton of the porous body, the physical and chemical properties of the surface and the interior can be made uniform, so that the swelling and shrinkage can be achieved. The durability against is improved.

(Method for producing first monolithic ion exchanger)
The first monolith ion exchanger is prepared by preparing a water-in-oil emulsion by stirring a mixture of oil-soluble monomer, surfactant and water that does not contain ion-exchange groups, and then polymerizing the water-in-oil emulsion. Step I for obtaining a monolithic organic porous intermediate having a continuous macropore structure having a total pore volume of 5 to 16 ml / g, a vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, a vinyl monomer, Step II for preparing a mixture comprising an organic solvent and a polymerization initiator that dissolves the cross-linking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer. The mixture obtained in Step II is allowed to stand still and in Step I. Polymerization is performed in the presence of the obtained monolithic organic porous intermediate to obtain a thick organic porous body having a skeleton thicker than the skeleton of the organic porous intermediate. It is obtained by performing the IV step of introducing an ion exchange group into the thick organic porous material obtained in the step III.

  In the first method for producing a monolithic ion exchanger, the step I may be performed in accordance with the methods described in JP-A Nos. 2003-334560 and 2002-306976.

  In the production of the monolith intermediate of step I, the oil-soluble monomer that does not contain an ion exchange group includes, for example, an ion exchange group such as a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group, and is soluble in water. Low and lipophilic monomers may be mentioned. Preferable examples of these monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene, ethylene, propylene, isobutene, butadiene, ethylene glycol dimethacrylate, and the like. These monomers can be used alone or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and the content thereof is 0.3 to 50 mol%, preferably 0.3 to the total oil-soluble monomer. 5 mol% is preferable in that the mechanical strength necessary for introducing a large amount of ion-exchange groups in a later step can be obtained.

  The surfactant is not particularly limited as long as it can form a water-in-oil (W / O) emulsion when an oil-soluble monomer containing no ion exchange group and water are mixed, and sorbitan monooleate, Nonionic surfactants such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, polyoxyethylene sorbitan monooleate; potassium oleate Anionic surfactants such as sodium dodecylbenzenesulfonate and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride; amphoteric surfactants such as lauryldimethylbetaine can be used . These surfactants can be used alone or in combination of two or more. The water-in-oil emulsion refers to an emulsion in which an oil phase is a continuous phase and water droplets are dispersed therein. The amount of the surfactant added may vary depending on the type of oil-soluble monomer and the size of the target emulsion particles (macropores), but it cannot be generally stated, but the total amount of oil-soluble monomer and surfactant Can be selected within a range of about 2 to 70%.

  In Step I, a polymerization initiator may be used as necessary when forming a water-in-oil emulsion. As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. For example, azobisisobutyronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, Examples thereof include hydrogen oxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and tetramethylthiuram disulfide.

  The mixing method for mixing the oil-soluble monomer not containing an ion exchange group, a surfactant, water, and a polymerization initiator to form a water-in-oil emulsion is not particularly limited. Method of mixing at once, oil-soluble monomer, surfactant and oil-soluble polymerization initiator oil-soluble component and water or water-soluble polymerization initiator water-soluble component separately and uniformly dissolved, A method of mixing the components can be used. There is no particular limitation on the mixing apparatus for forming the emulsion, and a normal mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an appropriate apparatus may be selected to obtain the desired emulsion particle size. Moreover, there is no restriction | limiting in particular about mixing conditions, The stirring rotation speed and stirring time which can obtain the target emulsion particle size can be set arbitrarily.

  The monolith intermediate obtained in Step I has a continuous macropore structure. When this coexists in the polymerization system, a porous structure having a thick skeleton is formed using the structure of the monolith intermediate as a template. The monolith intermediate is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 50 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all the structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. In particular, when the total pore volume is as large as 10 to 16 ml / g, in order to maintain a continuous macropore structure, it is preferable to contain 2 mol% or more of cross-linked structural units. On the other hand, if it exceeds 50 mol%, the porous body becomes brittle and the flexibility is lost.

  The type of the polymer material of the monolith intermediate is not particularly limited, and examples thereof include the same materials as the monolith polymer material described above. Thereby, the same polymer can be formed in the skeleton of the monolith intermediate, and the skeleton can be thickened to obtain a monolith having a uniform skeleton structure.

  The total pore volume of the monolith intermediate is 5 to 16 ml / g, preferably 6 to 16 ml / g. If the total pore volume is too small, the total pore volume of the monolith obtained after polymerizing the vinyl monomer becomes too small, and the pressure loss during water passage becomes large, which is not preferable. On the other hand, if the total pore volume is too large, the structure of the monolith obtained after polymerizing the vinyl monomer deviates from the continuous macropore structure, which is not preferable. In order to make the total pore volume of the monolith intermediate within the above numerical range, the ratio of the monomer and water may be about 1: 5 to 1:20.

  Moreover, the average diameter of the opening (mesopore) which is an overlap part of a macropore and a macropore is 20-200 micrometers in a monolith intermediate body in a dry state. When the average diameter of the openings is less than 20 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss at the time of passing water becomes large, which is not preferable. On the other hand, if it exceeds 200 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, resulting in insufficient contact between the water to be treated and the monolith ion exchanger, resulting in a decrease in desalting efficiency. This is not preferable. Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.

  Step II consists of a vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, an organic solvent and a polymerization initiator that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer. A step of preparing a mixture of In addition, there is no order of I process and II process, II process may be performed after I process, and I process may be performed after II process.

  The vinyl monomer used in step II is not particularly limited as long as it is a lipophilic vinyl monomer containing a polymerizable vinyl group in the molecule and having high solubility in an organic solvent, but is allowed to coexist in the polymerization system. It is preferred to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate. Specific examples of these vinyl monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; α-olefins such as ethylene, propylene, 1-butene and isobutene; Diene monomers such as butadiene, isoprene and chloroprene; halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl such as vinyl acetate and vinyl propionate Esters: methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-methacrylic acid 2- Hexyl, cyclohexyl methacrylate, benzyl methacrylate, and (meth) acrylic monomer of glycidyl methacrylate. These monomers can be used alone or in combination of two or more. The vinyl monomer suitably used in the present invention is an aromatic vinyl monomer such as styrene or vinyl benzyl chloride.

  The added amount of these vinyl monomers is 3 to 40 times, preferably 4 to 30 times, by weight with respect to the monolith intermediate coexisting during polymerization. If the amount of vinyl monomer added is less than 3 times that of the porous material, the resulting monolith skeleton (the thickness of the monolith skeleton wall) cannot be increased, and the adsorption capacity per volume and the volume after introduction of ion-exchange groups. Since the ion exchange capacity per unit becomes small, it is not preferable. On the other hand, if the amount of vinyl monomer added exceeds 40 times, the opening diameter becomes small, and the pressure loss during water passage becomes large, which is not preferable.

  As the crosslinking agent used in step II, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis. The amount of the crosslinking agent used is preferably 0.3 to 50 mol%, particularly 0.3 to 5 mol%, based on the total amount of the vinyl monomer and the crosslinking agent. When the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, if it exceeds 50 mol%, the brittleness of the monolith proceeds and the flexibility is lost, and the introduction amount of ion exchange groups is reduced. The monolith intermediate coexisting during polymerization of the vinyl monomer / crosslinking agent is preferably used so as to be approximately equal to the crosslinking density. If the amounts used of both are too large, the crosslink density distribution is biased in the produced monolith, and cracks are likely to occur during the ion exchange group introduction reaction.

  The organic solvent used in Step II is an organic solvent that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer. In other words, it is a poor solvent for the polymer formed by polymerization of the vinyl monomer. . Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples. For example, when the vinyl monomer is styrene, the organic solvent includes methanol, ethanol, propanol, butanol, Alcohols such as hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, ethylene glycol, propylene glycol, tetramethylene glycol, glycerin; diethyl ether, ethylene glycol dimethyl ether, cellosolve, methyl cellosolve, butyl cellosolve, polyethylene glycol, polypropylene Chain (poly) ethers such as glycol and polytetramethylene glycol; hexane, heptane, octane, isooctane, decane, dode Chain saturated hydrocarbons such as down, ethyl acetate, isopropyl acetate, cellosolve acetate, esters such as ethyl propionate. Moreover, even if it is a good solvent of polystyrene like a dioxane, THF, and toluene, when it is used with the said poor solvent and the usage-amount is small, it can be used as an organic solvent. These organic solvents are preferably used so that the concentration of the vinyl monomer is 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the vinyl monomer concentration is less than 30% by weight, the polymerization rate is lowered, or the monolith structure after polymerization deviates from the range of the present invention. On the other hand, if the vinyl monomer concentration exceeds 80% by weight, the polymerization may run away, which is not preferable.

  As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator is preferably oil-soluble. Specific examples of the polymerization initiator used in the present invention include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid) 1,1′-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide and the like. The amount of the polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but can be used in a range of about 0.01 to 5% with respect to the total amount of vinyl monomer and crosslinking agent.

  In step III, the mixture obtained in step II is allowed to stand and polymerize in the presence of the monolith intermediate obtained in step I to obtain a thick monolith having a skeleton thicker than the skeleton of the monolith intermediate. It is a process to obtain. The monolith intermediate used in the step III plays a very important role in creating the monolith having the novel structure of the present invention. As disclosed in JP-A-7-501140 and the like, when a vinyl monomer and a crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolith intermediate, a particle aggregation type monolithic organic porous material is obtained. The body is obtained. On the other hand, when a monolith intermediate having a continuous macropore structure is present in the polymerization system as in the present invention, the structure of the monolith after polymerization changes dramatically, the particle aggregation structure disappears, and the above-mentioned thick monolith is lost. Is obtained. The reason for this has not been elucidated in detail, but in the absence of a monolith intermediate, the cross-linked polymer produced by polymerization precipitates and precipitates in the form of particles, while a particle aggregate structure is formed. When a porous body (intermediate) is present in the system, the vinyl monomer and the cross-linking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous body, and polymerization proceeds in the porous body to obtain a thick skeleton monolith. It is thought that. Although the opening diameter is narrowed by the progress of the polymerization, since the total pore volume of the monolith intermediate is large, an appropriate opening diameter can be obtained even if the skeleton becomes thick.

  The internal volume of the reaction vessel is not particularly limited as long as it is large enough to allow the monolith intermediate to exist in the reaction vessel. When the monolith intermediate is placed in the reaction vessel, there is a gap around the monolith in plan view. Or a monolith intermediate in the reaction vessel with no gap. Of these, the thick monolith after polymerization is not pressed from the inner wall of the container and enters the reaction container without any gap, and the monolith is not distorted, and the reaction raw materials are not wasted and efficient. Even when the internal volume of the reaction vessel is large and there are gaps around the monolith after polymerization, the vinyl monomer and the crosslinking agent are adsorbed and distributed on the monolith intermediate, so the gaps in the reaction vessel A particle aggregate structure is not generated in the portion.

  In step III, the monolith intermediate is placed in a reaction vessel impregnated with the mixture (solution). As described above, the blending ratio of the mixture obtained in Step II and the monolith intermediate is 3 to 40 times by weight, preferably 4 to 30 times by weight, relative to the monolith intermediate. It is suitable to mix. Thereby, it is possible to obtain a monolith having a thick skeleton while having an appropriate opening diameter. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that has been allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate.

  Various polymerization conditions can be selected depending on the type of monomer and the type of initiator. For example, when 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as initiators In a sealed container under an inert atmosphere, heat polymerization may be performed at 30 to 100 ° C. for 1 to 48 hours. By heat polymerization, the vinyl monomer adsorbed and distributed on the skeleton of the monolith intermediate and the cross-linking agent are polymerized in the skeleton to thicken the skeleton. After completion of the polymerization, the contents are taken out and extracted with a solvent such as acetone for the purpose of removing unreacted vinyl monomer and organic solvent to obtain a thick monolith.

  Next, after producing a monolith by the above method, a method of introducing an ion exchange group is preferable in that the porous structure of the resulting monolith ion exchanger can be strictly controlled.

  There is no restriction | limiting in particular as a method to introduce | transduce an ion exchange group into the said monolith, Well-known methods, such as a polymer reaction and graft polymerization, can be used. For example, as a method of introducing a sulfonic acid group, if the monolith is a styrene-divinylbenzene copolymer, etc., a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid or fuming sulfuric acid; A method of grafting a sodium styrenesulfonate or acrylamido-2-methylpropanesulfonic acid by introducing a mobile group into the skeleton surface or inside the skeleton; Similarly, after graft polymerization of glycidyl methacrylate, a sulfonic acid group is introduced by functional group conversion. And the like. As a method for introducing a quaternary ammonium group, if the monolith is a styrene-divinylbenzene copolymer or the like, a method of introducing a chloromethyl group with chloromethyl methyl ether or the like and then reacting with a tertiary amine; A method in which chloromethylstyrene and divinylbenzene are produced by copolymerization and reacted with a tertiary amine; N, N, N-trimethylammonium is introduced into the monolith by introducing radical initiation groups and chain transfer groups uniformly into the skeleton surface and inside the skeleton. Examples include a method of graft polymerization of ethyl acrylate and N, N, N-trimethylammoniumpropylacrylamide; a method of grafting glycidyl methacrylate in the same manner and then introducing a quaternary ammonium group by functional group conversion. Examples of the method for introducing betaine include a method in which a tertiary amine is introduced into a monolith by the above method and then introduced by reacting with monoiodoacetic acid. Among these methods, the method of introducing a sulfonic acid group includes a method of introducing a sulfonic acid group into a styrene-divinylbenzene copolymer using chlorosulfuric acid, and a method of introducing a quaternary ammonium group includes styrene. -Introducing a chloromethyl group into the divinylbenzene copolymer with chloromethyl methyl ether, etc., then reacting with a tertiary amine, or producing a monolith by copolymerization of chloromethylstyrene and divinylbenzene and reacting with a tertiary amine The method is preferable in that the ion exchange group can be introduced uniformly and quantitatively. The ion exchange groups to be introduced include cation exchange groups such as carboxylic acid groups, iminodiacetic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphoric ester groups; quaternary ammonium groups, tertiary amino groups, and secondary amino groups. Groups, primary amino groups, polyethyleneimine groups, tertiary sulfonium groups, phosphonium groups and the like.

  Since the ion exchange group is introduced into the thick monolith, the first monolith ion exchanger swells greatly, for example, 1.4 to 1.9 times as thick as the monolith. That is, the degree of swelling is much greater than that obtained by introducing an ion exchange group into a conventional monolith described in JP-A-2002-306976. For this reason, even if the opening diameter of the thick monolith is small, the opening diameter of the monolith ion exchanger generally increases at the above magnification. In addition, the total pore volume does not change even when the opening diameter increases due to swelling. Therefore, the first monolith ion exchanger has a high mechanical strength because it has a thick bone skeleton despite the remarkably large opening diameter.

<Description of Second Monolith Ion Exchanger>
The second monolith ion exchanger is a tertiary having a thickness of 1 to 60 μm made of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit among all the structural units into which ion exchange groups are introduced. A co-continuous structure comprising an originally continuous skeleton and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, and the total pore volume is 0.5 to 5 ml / g Yes, the ion exchange capacity per volume in a water-wet state is 0.3 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger.

  The second monolith ion exchanger has a three-dimensional continuous skeleton having an average thickness of 1 to 60 μm, preferably 3 to 58 μm in a water-filled state in which ion exchange groups are introduced, and an average diameter between the skeletons. It is a co-continuous structure composed of three-dimensionally continuous pores of 10 to 100 μm, preferably 15 to 90 μm, particularly 20 to 80 μm in the water state. That is, as shown in the schematic diagram of FIG. 6, the co-continuous structure is a structure 60 in which a continuous skeleton phase 61 and a continuous vacancy phase 62 are intertwined and both are three-dimensionally continuous. The continuous vacancies 62 have higher continuity of vacancies than the conventional open-cell monolith and particle aggregation monolith, and the size of the vacancies is not biased. Therefore, an extremely uniform ion adsorption behavior can be achieved. Moreover, since the skeleton is thick, the mechanical strength is high.

  The skeleton thickness and pore diameter of the second monolith ion exchanger are larger than the monolith skeleton thickness and pore diameter because the entire monolith swells when an ion exchange group is introduced into the monolith. It becomes. These continuous pores have higher continuity of pores and are not biased in size compared to conventional open-cell monolithic organic porous ion exchangers and particle-aggregated monolithic organic porous ion exchangers. Therefore, extremely uniform ion adsorption behavior can be achieved. If the diameter of the three-dimensionally continuous pores is less than 10 μm, the pressure loss during passage of the fluid increases, which is not preferable. If it exceeds 100 μm, the contact between the water to be treated and the organic porous ion exchanger Becomes unsatisfactory, and as a result, the ion exchange characteristics become non-uniform. Further, if the thickness of the skeleton is less than 1 μm, it is not preferable because defects such as a decrease in ion exchange capacity per volume and a decrease in mechanical strength occur. On the other hand, if the skeleton thickness is too large, This is not preferable because the uniformity of the exchange characteristics is lost.

  The average diameter of the pores of the continuous structure in the water-filled state is a value calculated by multiplying the average diameter of the pores of the dry monolith ion exchanger measured by a known mercury intrusion method and the swelling ratio. It is. Specifically, the water state monolith ion exchanger has a diameter of x2 (mm), the water state monolith ion exchanger is dried, and the resulting dry state monolith ion exchanger has a diameter y2 ( mm), and when the average diameter of the pores when the dried monolith ion exchanger was measured by the mercury intrusion method was z2 (μm), The average diameter (μm) is calculated by the following formula: “Average diameter (μm) of water state of pores of monolith ion exchanger = z2 × (x2 / y2)” In addition, the average diameter of the pores of the dried monolith before introduction of the ion exchange groups, and the swelling rate of the water-borne monolith ion exchanger with respect to the dried monolith when the ion exchange groups are introduced into the dried monolith. If it is known, the average diameter of the water state of the pores of the monolith ion exchanger can also be calculated by multiplying the average diameter of the pores of the monolith in the dry state by the swelling rate. In addition, the average thickness of the skeleton of the continuous structure in the water state is SEM observation of the monolith ion exchanger in the dry state at least three times, and the thickness of the skeleton in the obtained image is measured. It is a value calculated by multiplying the average value by the swelling rate. Specifically, the water state monolith ion exchanger has a diameter of x3 (mm), the water state monolith ion exchanger is dried, and the resulting dry state monolith ion exchanger has a diameter of y3 ( SEM observation of this dried monolith ion exchanger at least three times, the thickness of the skeleton in the obtained image was measured, and the average value was z3 (μm). The average thickness (μm) of the skeleton of the continuous structure of the ion exchanger in the water state is expressed by the following formula: “average thickness (μm) of the hydrated state of the skeleton of the continuous structure of the monolith ion exchanger = z3 × (X3 / y3) ". In addition, the average thickness of the skeleton of the dried monolith before introduction of the ion exchange groups, and the swelling rate of the water-borne monolith ion exchanger with respect to the dried monolith when the ion exchange groups are introduced into the dried monolith. If it is known, the average thickness of the monolith ion exchanger skeleton can be calculated by multiplying the average thickness of the skeleton of the monolith in the dry state by the swelling rate. The skeleton has a rod-like shape and a circular cross-sectional shape, but may have a cross-section with a different diameter such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.

  If the thickness of the three-dimensional continuous rod-like skeleton is less than 10 μm, the second monolithic ion exchanger is not preferable because the ion exchange capacity per volume decreases, and if it exceeds 100 μm, the desalting characteristics This is not preferable because the uniformity of the film is lost. The definition and measurement method of the wall of the monolith ion exchanger are the same as those of the monolith.

  The second monolith ion exchanger has a total pore volume of 0.5 to 5 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of fluid permeation increases, which is not preferable. Further, the amount of permeated fluid per unit cross-sectional area decreases, and the processing capacity decreases. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the ion exchange capacity per volume decreases, which is not preferable. If the size of the three-dimensionally continuous pores and the total pore volume are in the above ranges, the contact with the fluid is extremely uniform and the contact area is large, so the ion exchange zone length is short and low pressure loss. Become. The total pore volume of the monolith (monolith intermediate, monolith, monolith ion exchanger) is the same in the dry state and in the water state.

  The pressure loss when water was permeated through the second monolith ion exchanger was the pressure loss when water was passed through a column filled with 1 m of a porous material at a water flow rate (LV) of 1 m / h (hereinafter referred to as “pressure loss”). And “differential pressure coefficient”) in the range of 0.001 to 0.5 MPa / m · LV, particularly 0.001 to 0.1 MPa / m · LV. If the permeation rate and the total pore volume are within this range, when this is used as part of the mixed ion exchanger of an electrical deionized water production device, pressure loss during water flow is suppressed, and conductivity and treatment are reduced. Improve water quality.

  In the second monolith ion exchanger, the material constituting the skeleton of the co-continuous structure is 0.3 to 5 mol%, preferably 0.5 to 3.0 mol% of the crosslinked structural unit in all the structural units. It is an aromatic vinyl polymer containing and is hydrophobic. If the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 5 mol%, the structure of the porous body tends to deviate from the bicontinuous structure. There is no restriction | limiting in particular in the kind of this aromatic vinyl polymer, For example, a polystyrene, poly ((alpha) -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene etc. are mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, a styrene-divinylbenzene copolymer is used because of its ease of forming a co-continuous structure, ease of introduction of ion exchange groups, high mechanical strength, and high stability against acids and alkalis. And vinylbenzyl chloride-divinylbenzene copolymer is preferred.

  The second monolith ion exchanger has an ion exchange capacity of 0.3 to 5 mg equivalent / ml cation exchange capacity per volume in a wet state of water. In the conventional monolithic organic porous ion exchanger having a continuous macropore structure different from the present invention as described in JP-A-2002-306976, in order to achieve a low pressure loss that is practically required, When the opening diameter is increased, the total pore volume is increased accordingly, so that the ion exchange capacity per volume is decreased, and the total pore volume is decreased in order to increase the exchange capacity per volume. In addition, since the opening diameter is reduced, the pressure loss increases. On the other hand, since the monolith ion exchanger of the present invention has high continuity and uniformity of three-dimensionally continuous pores, the pressure loss does not increase so much even if the total pore volume is reduced. Therefore, the ion exchange capacity per volume can be dramatically increased while keeping the pressure loss low, and the quality of treated water can be improved. The ion exchange capacity per weight in the dry state of the second monolith ion exchanger is not particularly limited, but the ion exchange groups are uniformly introduced to the skeleton surface and the skeleton inside the porous body. 5 mg equivalent / g. The ion exchange capacity of a porous body in which ion exchange groups are introduced only on the surface of the skeleton cannot be determined unconditionally depending on the kind of the porous body or ion exchange groups, but is at most 500 μg equivalent / g.

  The ion exchange group in the second monolith ion exchanger is the same as the ion exchange group in the first monolith ion exchanger, and the description thereof is omitted. In the second monolith ion exchanger, the introduced ion exchange groups are uniformly distributed not only on the surface of the porous body but also within the skeleton of the porous body. The definition of the uniform distribution is the same as the definition of the uniform distribution of the first monolith ion exchanger.

(Method for producing second monolith ion exchanger)
The second monolith ion exchanger prepares a water-in-oil emulsion by stirring a mixture of oil-soluble monomer, surfactant and water that does not contain ion-exchange groups, and then polymerizes the water-in-oil emulsion. Step I for obtaining a monolithic organic porous intermediate having a continuous macropore structure having a total pore volume of more than 16 ml / g and 30 ml / g or less, an aromatic vinyl monomer, and at least two or more vinyl groups in one molecule From an organic solvent and a polymerization initiator in which 0.3 to 5 mol% of the cross-linking agent, aromatic vinyl monomer and cross-linking agent dissolve but the polymer formed by polymerization of the aromatic vinyl monomer does not dissolve in the total oil-soluble monomer having Step II for preparing the mixture, the mixture obtained in Step II is allowed to stand, and polymerization is performed in the presence of the monolithic organic porous intermediate obtained in Step I. III to obtain a continuous structure, obtained by performing the IV step of introducing ion exchange groups to resulting co-continuous structure in the step III.

  What is necessary is just to perform the I process of obtaining the monolith intermediate body in a 2nd monolith ion exchanger based on the method of Unexamined-Japanese-Patent No. 2002-306976.

  That is, in the step I, as the oil-soluble monomer not containing an ion exchange group, for example, it does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group, has low solubility in water, and is lipophilic. These monomers are mentioned. Specific examples of these monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; α-olefins such as ethylene, propylene, 1-butene and isobutene; butadiene Diene monomers such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethyl methacrylate Sill, cyclohexyl methacrylate, benzyl methacrylate, and (meth) acrylic monomer of glycidyl methacrylate. Among these monomers, preferred are aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene and the like. These monomers can be used alone or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and its content is 0.3 to 5 mol%, preferably 0.3 to the total oil-soluble monomer. 3 mol% is preferable in that a mechanical strength necessary for introducing a large amount of ion-exchange groups in a later step can be obtained.

  The surfactant is the same as the surfactant used in step I of the first monolith ion exchanger, and the description thereof is omitted.

  In Step I, a polymerization initiator may be used as necessary when forming a water-in-oil emulsion. As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2 , 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis ( 4-cyanovaleric acid), 1,1'-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide, hydrogen peroxide-ferrous chloride Sodium persulfate-sodium acid sodium sulfite and the like.

  As a mixing method when an oil-soluble monomer not containing an ion exchange group, a surfactant, water and a polymerization initiator are mixed to form a water-in-oil emulsion, in the step I of the first monolith ion exchanger This is the same as the mixing method, and the description thereof is omitted.

  In the second method for producing a monolith ion exchanger, the monolith intermediate obtained in the step I is an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 5 mol%, preferably 0.3 to 3 mol% of crosslinked structural units with respect to all structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 5 mol%, the structure of the monolith tends to deviate from the co-continuous structure, which is not preferable. In particular, when the total pore volume is as small as 16 to 20 ml / g in the present invention, the cross-linking structural unit is preferably less than 3 mol in order to form a co-continuous structure.

  The type of the polymer material of the monolith intermediate is the same as the type of the polymer material of the monolith intermediate of the first monolith ion exchanger, and the description thereof is omitted.

  The total pore volume of the monolith intermediate is more than 16 ml / g and not more than 30 ml / g, preferably 6-25 ml / g. In other words, this monolith intermediate basically has a continuous macropore structure, but the opening (mesopore) that is the overlapping part of the macropore and the macropore is remarkably large, so that the skeleton constituting the monolith structure is primary from the two-dimensional wall surface. It has a structure as close as possible to the original rod-like skeleton. When this coexists in the polymerization system, a porous body having a co-continuous structure is formed using the structure of the monolith intermediate as a template. If the total pore volume is too small, the structure of the monolith obtained after polymerizing the vinyl monomer is not preferable because it changes from a co-continuous structure to a continuous macropore structure. On the other hand, if the total pore volume is too large, This is not preferable because the mechanical strength of the monolith obtained after polymerizing the vinyl monomer is lowered and the ion exchange capacity per volume is lowered. In order to make the total pore volume of the monolith intermediate within a specific range of the second monolith ion exchanger, the ratio of monomer to water may be approximately 1:20 to 1:40.

  Moreover, the average diameter of the opening (mesopore) which is an overlap part of a macropore and a macropore is a monolith intermediate body is 5-100 micrometers in a dry state. When the average diameter of the openings is less than 5 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer is reduced, and the pressure loss during water passage is increased, which is not preferable. On the other hand, if it exceeds 100 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, and the contact between the fluid and the monolith ion exchanger becomes insufficient, resulting in a decrease in ion exchange characteristics. Therefore, it is not preferable. Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.

  In the second method for producing a monolithic ion exchanger, the step II includes 0.3 to 5 mol% of a crosslinking agent in the aromatic vinyl monomer and the total oil-soluble monomer having at least two or more vinyl groups in one molecule. This is a step of preparing a mixture comprising an organic solvent and a polymerization initiator that dissolves the aromatic vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer. In addition, there is no order of I process and II process, II process may be performed after I process, and I process may be performed after II process.

  In the second method for producing a monolithic ion exchanger, the aromatic vinyl monomer used in step II includes a lipophilic aromatic vinyl monomer that contains a polymerizable vinyl group in the molecule and has high solubility in an organic solvent. If it is, there is no particular limitation, but it is preferable to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate coexisting in the polymerization system. Specific examples of these vinyl monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl, vinyl naphthalene and the like. These monomers can be used alone or in combination of two or more. Aromatic vinyl monomers preferably used in the present invention are styrene, vinyl benzyl chloride and the like.

  The amount of these aromatic vinyl monomers added is 5 to 50 times, preferably 5 to 40 times, by weight with respect to the monolith intermediate coexisting during polymerization. If the amount of aromatic vinyl monomer added is less than 5 times that of the porous material, the rod-shaped skeleton cannot be made thicker, the ion exchange capacity per volume after the introduction of ion exchange groups is reduced, and the conductivity and treated water quality are reduced. Can not be increased.

  As the crosslinking agent used in step II, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis. The amount of the crosslinking agent used is 0.3 to 5 mol%, particularly 0.3 to 3 mol%, based on the total amount of vinyl monomer and crosslinking agent (total oil-soluble monomer). When the amount of the crosslinking agent used is less than 0.3 mol%, it is not preferable because the mechanical strength of the monolith is insufficient. On the other hand, when the amount is too large, the brittleness of the monolith proceeds and the flexibility is lost. This is not preferable because a problem arises in that the amount of introduction of is reduced. In addition, it is preferable to use the said crosslinking agent usage-amount so that it may become substantially equal to the crosslinking density of the monolith intermediate body coexisted at the time of vinyl monomer / crosslinking agent polymerization. If the amounts used of both are too large, the crosslink density distribution is biased in the produced monolith, and cracks are likely to occur during the ion exchange group introduction reaction.

  The organic solvent used in step II is an organic solvent that dissolves the aromatic vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer, in other words, is formed by polymerization of the aromatic vinyl monomer. It is a poor solvent for polymers. Since the organic solvent varies greatly depending on the type of the aromatic vinyl monomer, it is difficult to list general specific examples. For example, when the aromatic vinyl monomer is styrene, the organic solvent includes methanol, ethanol, Alcohols such as propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, tetramethylene glycol; chain structures such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (Poly) ethers; chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane; ethyl acetate, isopropyl acetate, cellosolve acetate, propionic acid Examples include esters such as ethyl. Moreover, even if it is a good solvent of polystyrene like a dioxane, THF, and toluene, when it is used with the said poor solvent and the usage-amount is small, it can be used as an organic solvent. These organic solvents are preferably used so that the concentration of the aromatic vinyl monomer is 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the aromatic vinyl monomer concentration becomes less than 30% by weight, the polymerization rate is lowered, or the monolith structure after polymerization deviates from the scope of the present invention, which is not preferable. On the other hand, if the concentration of the aromatic vinyl monomer exceeds 80% by weight, the polymerization may run away, which is not preferable.

  The polymerization initiator is the same as the polymerization initiator used in Step II of the first monolith ion exchanger, and the description thereof is omitted.

  In the second method for producing a monolith ion exchanger, in the step III, the mixture obtained in the step II is allowed to stand, and polymerization is performed in the presence of the monolith intermediate obtained in the step I. This is a process of changing the continuous macropore structure of the body to a co-continuous structure to obtain a monolith with a bone skeleton. The monolith intermediate used in the step III plays a very important role in creating the monolith having the novel structure of the present invention. As disclosed in JP-A-7-501140 and the like, when a vinyl monomer and a crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolith intermediate, a particle aggregation type monolithic organic porous material is obtained. The body is obtained. On the other hand, when a monolith intermediate having a specific continuous macropore structure is present in the polymerization system as in the second monolith of the present invention, the structure of the monolith after the polymerization changes dramatically and the particle aggregation structure disappears. Thus, a monolith having the above-described bicontinuous structure can be obtained. The reason for this has not been elucidated in detail, but in the absence of a monolith intermediate, the cross-linked polymer produced by polymerization precipitates and precipitates in the form of particles, while a particle aggregate structure is formed. When a porous body (intermediate) having a large total pore volume is present in the system, the vinyl monomer and the crosslinking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous body, and polymerization proceeds in the porous body. It is considered that the skeleton constituting the monolith structure is changed from a two-dimensional wall surface to a one-dimensional rod-like skeleton to form a monolithic organic porous body having a co-continuous structure.

  The internal volume of the reaction vessel is the same as the description of the internal volume of the reaction vessel of the first monolith ion exchanger, and the description thereof is omitted.

  In step III, the monolith intermediate is placed in a reaction vessel impregnated with the mixture (solution). As described above, the blending ratio of the mixture obtained in Step II and the monolith intermediate is 5 to 50 times, preferably 5 to 40 times the weight of the aromatic vinyl monomer added to the monolith intermediate. It is preferable to blend them as described above. Thereby, it is possible to obtain a monolith having a co-continuous structure in which pores of an appropriate size are three-dimensionally continuous and a thick skeleton is three-dimensionally continuous. In the reaction vessel, the aromatic vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that is allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate.

  The basic structure of a monolith having a co-continuous structure is a three-dimensional continuous skeleton having an average thickness of 0.8 to 40 μm in a dry state and a three-dimensional continuous sky having a diameter of 8 to 80 μm between the skeletons. This is a structure in which holes are arranged. The average diameter of the three-dimensionally continuous pores can be obtained as a maximum value of the pore distribution curve by measuring the pore distribution curve by the mercury intrusion method. The thickness of the skeleton of the monolith may be calculated by performing SEM observation at least three times and measuring the average thickness of the skeleton in the obtained image. A monolith having a co-continuous structure has a total pore volume of 0.5 to 5 ml / g.

  The polymerization conditions are the same as the description of the polymerization conditions in step III of the first monolith ion exchanger, and the description thereof is omitted.

  In the step IV, the method for introducing an ion exchange group into a monolith having a co-continuous structure is the same as the method for introducing an ion exchange group into a monolith in the first monolith ion exchanger, and the description thereof is omitted.

  Since the ion exchange group is introduced into the bilithic monolith, the second monolith ion exchanger swells greatly, for example, 1.4 to 1.9 times that of the monolith. Further, the total pore volume does not change even if the pore diameter becomes larger due to swelling. Therefore, the second monolith ion exchanger has a high mechanical strength because it has a thick bone skeleton even though the size of three-dimensionally continuous pores is remarkably large. Moreover, since the skeleton is thick, the ion exchange capacity per volume in a water-wet state can be increased, and the conductivity and the quality of treated water can be improved.

  In this invention, it does not restrict | limit especially as a granular ion exchange resin, The well-known ion exchange resin used for a water treatment is mentioned.

  Although it does not restrict | limit especially as a mixture of a monolith and an ion exchange resin, The layered body by which the monolith phase and the ion exchange resin phase were laminated | stacked in the water flow direction (direction in which discharge | emission ion migrates) is mentioned. Since the monolith and the ion exchange resin layered body are a sponge-like integrated structure, the monolith is not mixed with the ion exchange resin and can be filled in phase without using partition means such as an ion exchange membrane in the container. . The volume ratio of the monolith phase and the ion exchange resin phase in the layered body is not particularly limited, and is appropriately determined depending on the type of ion exchange group, the purpose of treating the water to be treated, and the like. Further, the laminated structure of the layered body is not particularly limited, and the monolith phase and the ion exchange resin phase, and the ion exchange resin phase and the monolith phase in order from the ion exchange membrane on one side to the ion exchange membrane on the other side. Examples of the layer structure include a monolith phase, an ion exchange resin phase and a monolith phase, a three layer structure of an ion exchange resin phase, a monolith phase and an ion exchange resin phase; and a four layer structure which is a repetition of a monolith phase and an ion exchange resin phase. Among these, the configuration in which the monolith phase is arranged in the vicinity of the treated water inlet improves the removal rate of hardness components such as calcium ions in the decation chamber, and removes anions such as carbonic acid and silica in the deanion chamber. Is preferable in terms of improvement. In the deanion chamber, it is preferable to dispose a cation monolith in the vicinity of the treated water outlet in that a small amount of cations that could not be removed in the decation chamber can be reliably removed.

The ionic form of the mixture of the monolith and the ion exchange resin is not particularly limited, but a salt form and a regenerated form mixture are preferred in that they can alleviate swelling and shrinkage associated with the ion exchange reaction. In the present invention, the swelling / shrinkage mitigating effect of the monolith / ion exchange resin mixture alone is not sufficient, and the physical expansion / contraction effect of the monolith is added to ensure adhesion in the deionization chamber. . The expansion and contraction of the mixture of monolith and ion exchange resin will be described by taking a cation cell as an example. The cation cell of FIG. 13A is composed of 40 ml of R—Na granular cation exchange resin (cross section 4 × 5 = 20 cm ² , length between electrodes 2 cm) in order from the cathode side to the anode side, RH granular cation exchange resin. 80 ml (cross section 4 × 5 = 20 cm ² , electrode length 4 cm) and R—Na cation monolith 40 ml (cross section 4 × 5 = 20 cm ² , electrode length 2 cm) are filled. When continuous water flow / continuous regeneration is performed for the cation cell, usually, the R—Na particulate cation exchange resin is partially regenerated and swells, and the RH particulate cation exchange resin does not change, and the R—Na cation monolith is not changed. Regenerates and swells. At this time, although the cation monolith regenerated from R—Na to R—H swells, it crushes into a sponge shape (concave shape) and absorbs the swelling of the R—Na granular cation exchange resin. The degree is improved and the balance fits in the container (FIG. 13B). On the other hand, when the above-mentioned cation cell is subjected to continuous water flow / regeneration, the ion load of the water to be treated is high and the ion accumulation tendency is more balanced than the initial filling state. Side) to the treated water outlet (anode, regeneration side), and the continuous treatment is performed with the ion exchanger length extended. In this case, the R—Na particulate cation exchange resin does not change, the RH particulate cation exchange resin partially changes into a salt form and contracts, and the R—Na cation monolith is regenerated to RH and swells. At this time, the cation monolith regenerated from R—Na to R—H compensates for the volume reduction of the R—H granular cation exchange resin. (FIG. 13C). In this example, the R—Na granular cation exchange resin and the R—H granular cation exchange resin are described as being packed in layers, but the present invention is not limited to this, and may be used in a mixed manner. Has the effect of.

  In the present invention, the water to be treated is intended for deionization treatment and is not particularly limited as long as it does not contain turbidity. For example, industrial water or city water having a turbidity of about 1 degree or less. Can be mentioned.

  Next, the electric deionized water production apparatus according to the first embodiment of the present invention will be described with reference to FIG. FIG. 14 is a schematic diagram showing the structure of the electric deionized water production apparatus of this example. 14A is an anion cell 20a that mainly removes anionic impurities from water to be treated, and a cation cell 20b that mainly removes cationic impurities from the treated water of the anion cell 20a. It consists of

  The anion cell 20a includes an anion monolith 14 and an anion exchange resin 11 in order from the one anion exchange membrane 2 side into a deionization chamber partitioned by the one anion exchange membrane 2 and the other cation exchange membrane 1. To form a deanion chamber 7 and an anode 10 outside the anion exchange membrane 2 on one side and a cathode 9 outside the cation exchange membrane 1 on the other side. Supplied from the inlet 3a in the vicinity of the anion exchange membrane 2 on one side (anode side) in the deanion ion chamber 7, and in the vicinity of the cation exchange membrane 1 on the other side (cathode side) in the deanion ion chamber 7. The first treated water is obtained from the outlet 4a. That is, the water flow direction in the anion cell 20a of the anion cell 20a is from the left to the right, which is the solid arrow direction in FIG. The filling ratio of the anion monolith 14 and the anion exchange resin 11 can be arbitrarily determined depending on the properties of the water to be treated, but preferably the monolith: ion exchange resin is 1: 0.5 to 1:10 by volume. .

  On the other hand, the cation cell 20b includes a cation monolith 13 and a cation exchange resin in order from the cation exchange membrane 1 to the deionization chamber partitioned by the cation exchange membrane 1 on the one side and the cation exchange membrane 1 on the other side. 12, a decation chamber 6 is formed, a cathode 9 is arranged outside the cation exchange membrane 1 on one side, and an anode 10 is arranged outside the cation exchange membrane 1 on the other side, and an anion cell 20a. Of the treated water (first treated water) from the inlet 3b in the vicinity of the cation exchange membrane 1 on one side (cathode side) in the decation chamber 6 and the other side (anode) in the decation chamber 6 The treated water (second treated water) is obtained from the outlet 4b near the cation exchange membrane 1 on the side). That is, the water flow direction in the cation chamber 6 of the cation cell 20b is from the left to the right, which is the direction of the solid arrow in FIG. The filling ratio of the cation monolith 13 and the cation exchange resin 12 can be arbitrarily determined depending on the properties of the water to be treated, but preferably the monolith: ion exchange resin is 1: 0.5 to 1:10 by volume. .

  As the anion monolith 14 filled in the deanion chamber 7 of the anion cell 20a and the cation monolith 13 filled in the decation chamber 6 of the cation cell 20b, the above-described monolithic organic porous ion exchanger is used. Is preferred. Moreover, as the shape of the decation ion chamber 6 and the deanion ion chamber 7, if an electric field can be applied so that the ions to be excluded migrate in the direction opposite to the water flow direction in the mixed ion exchanger, Although not particularly limited, for example, a cylindrical shape or a rectangular parallelepiped shape is preferable from the viewpoint of ease of manufacturing the constituent members. Moreover, the distance to which the water to be treated moves, that is, the effective thickness of the mixed ion exchanger packed layer constituting the decation ion chamber 6 and the deanion chamber 7 is 20 to 600 mm, preferably 30 to 300 mm. This is preferable in that deionization can be reliably performed while suppressing the electric resistance value and the water flow differential pressure.

  Examples of the cation exchange membrane, the anion exchange membrane, the cathode, the anode, the arrangement form of the electrode and the ion exchange membrane, the arrangement form of the direct current, and the method of energizing the direct current include those described in JP-A-2003-334560. . In the anion cell 20a, a non-conductive spacer 8 such as a polyolefin mesh is interposed between the anode and the anion exchange membrane in order to avoid direct contact between them. Thereby, it is possible to prevent the deterioration of the anion exchange membrane due to the strong oxidizing action on the anode side.

  In the anion cell 20a and the cation cell 20b, the method for flowing into the mixed ion exchanger in the treated water and the method for collecting water from the mixed ion exchanger in the treated water are not particularly limited, and a container filled with the mixed ion exchanger. What is necessary is just to flow in treated water or flow out treated water from an inflow port or an outflow port installed in the vicinity of the ion exchange membrane. Also, for example, in order to form an even flow of water to be treated in the deionization chamber, the distribution pipes and water collection pipes having pores in the pipes are concentrically or equidistantly paralleled in line with the shape of the deionization chamber. Using a method of embedding in an ion exchanger, a method of cutting a groove in the monolith treated water collection section or the first treated water introduction / distribution section, and providing the monolith itself with a treated water collection function or a treated water distribution function Also good.

  In addition, the operation method of the electric deionized water production apparatus 20A of this example may be either continuous operation or intermittent operation. For example, the continuous operation method by continuous water flow and continuous energization of the water to be treated and the treatment target. Examples include an intermittent operation method in which water flow is stopped for a certain period of time and direct current is supplied only during the water stoppage time.

In the anion cell 20a, water to be treated is introduced from an inlet 3a in the vicinity of the anion exchange membrane 2 on the anode 10 side of the deanion chamber 7. Next, the water to be treated moves to the cathode 9 side while adsorbing and removing the anions Y ⁻ in the anion monolith 14 and the anion exchange resin 11, and serves as the first treated water in the cathode 9 side cation exchange membrane of the deanion chamber 7. 1 is discharged from the outlet 4a in the vicinity. Next, the first treated water is introduced into the vicinity of the cathode 9 side cation exchange membrane 1 in the decation chamber 6 of the cation cell 20b through the communication pipe 5a and the inlet 3b. Next, the first treated water, which is the treated water, moves to the anode 10 side while adsorbing and removing the cation X ⁺ in the cation monolith 13 and the cation exchange resin 12, and serves as the second treated water in the anode of the decation chamber 6. It is discharged from the 10-side cation exchange membrane 1 vicinity outlet 4b.

The anion Y ⁻ adsorbed on the anion monolith 14 and the anion exchange resin 11 in the deanion chamber 7 is electrically generated by a direct current applied between the cathode 9 and the anode 10 disposed at both ends of the deanion chamber 7. The anion Y ⁻ passes through the anion exchange membrane 2 on the anode 10 side and is discharged to the anode chamber (not shown). Similarly, the cation X ⁺ adsorbed by the cation monolith 13 and the cation exchange resin 12 in the decation chamber 6 is applied to the direct current applied between the cathode 9 and the anode 10 disposed at both ends of the decation chamber 6. Electrophoresis is caused by electric current, passes through the cation exchange membrane 1 on the cathode 9 side, and is discharged to the cathode chamber (not shown).

  The impurity anions discharged into the anode chamber flow in from the anode chamber inlet, are taken into the electrode water flowing out from the anode chamber outlet, and are discharged out of the system. Similarly, impurity cations discharged into the cathode chamber flow into the electrode chamber inlet, flow into the electrode water flowing out from the cathode chamber outlet, and are discharged out of the system. The electrode water may be made to flow partially through the four electrode chambers by branching off part of the water to be treated, or may flow through two systems of an anodic water system and a cathodic water system. Moreover, electrode water may be always flowed and may be appropriately flowed intermittently.

  In this method, in the anion cell 20a, an anionic monolith phase is arranged in the vicinity of the inlet of the water to be treated, so that the removal rate of anions such as carbonic acid and silica is improved. This is particularly effective when containing a large amount of carbonic acid. According to this apparatus, since the monolith and the ion exchange resin are mixed in layers in the cell, it is possible to compensate for the decrease in ion exchange capacity due to the use of the monolith. Further, the volume change due to the swelling and shrinkage reaction of the monolith and the ion exchange resin can be mitigated by the physical stretchability of the monolith, and the filling state in the deion exchange chamber can be kept uniform. Further, since the impurity cation and the impurity anion are separately discharged outside the apparatus, they are not mixed in the apparatus as in the conventional electric deionized water production apparatus, and calcium or Even when a hardness component such as magnesium is contained, no scale is generated in the apparatus.

  In addition to the above, for example, a method of treating the water to be treated with the cation cell 20b and then treating the treated water of the cation cell 20b with the anion cell 20a as the water passing method of the electric deionized water production apparatus 20A. Can do. According to this method, since water is first passed through the cation cell and calcium ions and magnesium ions are excluded, generation of scale in the anion cell 20a can be prevented. Further, in the cation cell 20b, a cation monolith is formed in the vicinity of the inlet of the water to be treated. Since the phases are arranged, the exclusion rate of calcium ions and magnesium ions is improved. For this reason, this method is effective when processing the to-be-processed water containing hardness components, such as calcium and magnesium.

  In the electric deionized water production apparatus 20A of the present example, the mixed ion exchanger filled in the deanion chamber 7 is different from the above-described form in that the other side of the anion exchange membrane 2 from the one side (anode side). Examples include a form in which the anion exchange resin and the cation monolith are filled in order toward the cation exchange membrane 1, a form in which the anion monolith, the anion exchange resin, and the cation monolith are filled. The ion exchange membrane on the cathode side is determined as a cation exchange membrane or an anion exchange membrane depending on the ion exchanger filled in the vicinity. When the anion exchange resin and the cation monolith are filled, they can be buffered by the physical stretchability of the cation monolith, the filling state in the deanion chamber can be kept uniform, and a simple polishing function can be provided. In addition, when an anion monolith, an anion exchange resin, and a cation monolith are filled in this order, the removal rate of impurity anions such as carbonic acid and silica can be increased, and a simple polishing function is provided. The filling state in the deanion chamber can be kept uniform by physical stretchability. Similarly, an appropriate ion exchanger can be selected for the mixed ion exchanger filled in the decation chamber 6 as well. Similarly, for these forms, a method of treating the treated water with the cation cell 20b and then treating the treated water of the cation cell 20b with the anion cell 20a can be employed.

  Next, an electric deionized water production apparatus according to a second embodiment of the present invention will be described with reference to FIG. FIG. 15 is a schematic view showing the structure of the electric deionized water production apparatus of this example. In FIG. 15, the same components as those of FIG. The electric deionized water production apparatus 20B of FIG. 15 is different from FIG. 14 in that one set of electrodes is omitted and a decation chamber and a deion chamber are provided between the pair of electrodes. That is, the electric deionized water production apparatus 20B of the present example is provided with the intermediate cation exchange membrane 1 between the cation exchange membrane 1 on one side and the anion exchange membrane 2 on the other side, and cation exchange on one side. A first deionization chamber partitioned by the membrane 1 and the intermediate cation exchange membrane 1 is filled with a cation monolith 13 and a cation exchange resin 12 to form a decation chamber 6, and an anion exchange membrane 2 on the other side and an intermediate The second deionization chamber partitioned by the cation exchange membrane 1 is filled with the anion exchange resin 11 and the anion monolith 14 from the intermediate cation exchange membrane 1 side to form the deanion ion chamber 7, and one side cation exchange is performed. A cathode 9 is arranged outside the membrane 1 and an anode 10 is arranged outside the anion exchange membrane 2 on the other side, and the anion exchange membrane 2 on the other side (anode side) in the deionized ion 7 chamber is treated water. The intermediate positive electrode in the deanion ion chamber 7 is supplied from the inlet 3a in the vicinity. The first treated water is obtained from the outlet 4a near the ion exchange membrane 1, and the first treated water is supplied from the inlet 3b near the cation exchange membrane 1 on one side (cathode side) in the decation chamber 6. Thus, the second treated water is obtained from the outlet 4b near the intermediate cation exchange membrane 1 in the decation chamber 6.

In electrodeionization water producing apparatus 20B, the for-treatment water which has flowed from the 10 side anion-exchange membrane 2 near the anode of Datsukage ion chamber 7 anion Y in the anion monolith 14 and anion exchange resin 11 ^- is adsorbed removed However, it moves to the intermediate cation exchange membrane 1 side and is discharged as first treated water from the intermediate cation exchange membrane 1 vicinity outlet 4b of the deanion ion chamber 7. Next, the first treated water is introduced into the decation chamber 6 from the vicinity of the cathode 9 side cation exchange membrane 1 in the decation chamber 6 through the communication pipe 5b. Next, the first treated water moves to the intermediate cation exchange membrane 1 side while adsorbing and removing the cation X ⁺ in the cation monolith 13 and the cation exchange resin 12, and serves as the second treated water in the middle of the decation chamber 6. It is discharged from the vicinity of the cation exchange membrane 1.

On the other hand, the cation X ⁺ adsorbed by the mixed cation exchanger in the decation chamber 6 is electrophoresed by a direct current applied between the cathode 9 and the anode 10 disposed at both ends of the apparatus 20B. Then, it passes through the cation exchange membrane 1 on the cathode 9 side and is discharged to the cathode chamber (not shown). Similarly, the anion Y ⁻ adsorbed on the mixed anion exchanger in the deanion chamber 7 is also electrophoresed by a direct current applied between the cathode 9 and the anode 10, and the anion on the anode 10 side. It passes through the ion exchange membrane 2 and is discharged to an anode chamber (not shown). That is, the direction of water flow in the deanion chamber 7 is from the right to the left, which is the direction of the solid line in FIG. In addition, the water flow direction in the decation ion chamber 6 is from the left to the right, which is the direction of the solid line, and the excluded cations migrate in the opposite direction to the water flow direction in the mixed ion exchanger. . The filling ratio of the monolith and the ion exchange resin in the decation chamber 6 and the deanion chamber 7 can be arbitrarily determined depending on the properties of the water to be treated, but preferably the monolith: ion exchange resin is in a volume ratio. 1: 0.5-1: 10. According to the electric deionized water production apparatus 20B of the second embodiment, the same effect as the electric deionized water production apparatus 20A of the first embodiment is obtained, and one set of electrodes is omitted. Thus, the device can be reduced in size and simplified.

  In addition to the above, as a water passing method of the electrical deionized water production apparatus 20B, for example, the water to be treated is treated in the decation chamber 6, and then the treated water in the decation chamber 6 is treated in the deanion chamber 7. Can be taken. According to this method, water is first passed through the decation ion chamber 6 to eliminate calcium ions and magnesium ions, so that scale generation in the deanion ion chamber 7 can be prevented. Since the cationic monolith phase is arranged in the vicinity, the exclusion rate of calcium ions and magnesium ions is improved. For this reason, it is effective when processing the to-be-processed water containing hardness components, such as calcium and magnesium.

  In the electric deionized water production apparatus 20B of this example, the mixed ion exchanger filled in the decation chamber 6 is not limited to the above-described form, but the intermediate ion exchange from the cation exchange membrane 1 on one side (cathode side). For example, a form in which the cation exchange resin and the anion monolith are filled in order toward the membrane 1 and a form in which the cation monolith, the cation exchange resin, and the anion monolith are filled are exemplified. The intermediate ion exchange membrane 1 is determined as a cation exchange membrane or an anion exchange membrane by an ion exchanger filled in the vicinity. When filled with a cation exchange resin and an anionic monolith, it can be buffered by the physical stretchability of the anionic monolith, the filling state in the decation chamber 6 can be kept uniform, and a simple polishing function can be provided. . In addition, when charged in the order of cation monolith, cation exchange resin, anion monolith, the removal rate of impurity cations including the above-mentioned hardness components such as calcium and magnesium can be increased, and a polishing function is provided. Can maintain a uniform filling state in the decation chamber 6 due to the physical stretchability of both monoliths. As for the mixed ion exchanger filled in the deanion chamber 7, an ion exchanger can be selected as appropriate. Similarly, for these forms, a method of treating the water to be treated in the decation chamber 6 and then treating the treated water in the decation chamber 6 in the deanion chamber 7 can be adopted.

  Next, an electric deionized water production apparatus according to a third embodiment of the present invention will be described with reference to FIG. FIG. 16 is a schematic view showing the structure of the electric deionized water production apparatus of this example. In FIG. 16, the same components as those in FIG. 15 are denoted by the same reference numerals, description thereof is omitted, and different points are mainly described. The electric deionized water production apparatus 20C of FIG. 16 is different from FIG. 15 in that both the intermediate cation exchange membrane 1 and the cation exchange resin are omitted. That is, the electric deionized water production apparatus 20C of this example is configured by disposing the anode 10 outside the anion exchange membrane 2 on one side and the cathode 9 outside the cation exchange membrane 1 on the other side. The anion monolith 14, the anion exchange resin 11, and the cation are sequentially arranged from the anion exchange membrane 2 side of one side (anode side) into the deionization chamber 15 partitioned by the anion exchange membrane 2 and the cation exchange membrane 1 on the other side. The deionization chamber 15 is configured by filling the monolith 13, and water to be treated is supplied from the inlet 3 c near the anion exchange membrane 2 on one side in the deionization chamber 15, and the other side in the deionization chamber 15 is supplied. The treated water is obtained from the outlet 4c near the cation exchange membrane 1. That is, the direction of water flow in the deionization chamber 15 is from left to right, which is the direction of the solid arrow in FIG.

In the electrical deionized water production apparatus 20 </ b> C, the water to be treated is introduced from the inlet 3 c in the vicinity of the anode 10 side anion exchange membrane 2 in the deionization chamber 15. Then, the water to be treated anion Y in the anion monolith 14 and anion exchange resin 11 ^- moved to while being adsorbed removed cathode 9 side, further the cathode 9 side while being adsorbed and removed cations X ⁺ in the cation monolith 13 And is discharged as treated water from an outlet 4c near the cathode 9 side cation exchange membrane 1 in the deionization chamber 15. According to the electric deionized water production apparatus 20C, the same effect as that of the electric deionized water production apparatus 20B can be obtained, and the intermediate cation membrane can be omitted to reduce the size and simplify the apparatus. In the case of the electric deionized water production apparatus 20C, the migration direction of the anion Y ⁻ is opposite to the water flow direction, and the migration direction of the cation X ⁺ is the same direction as the water flow direction.

In the electric deionized water production apparatus 20C, the mixed ion exchanger filled in the deionization chamber 15 is changed from the anion exchange membrane 2 on one side to the cation exchange membrane 1 on the other side in addition to the above-described form. The form which fills the anion exchange resin 11 and the cation monolith 13 in order toward this is mentioned. Similarly, the inflow location of the water to be treated is not limited to the above embodiment, and the water to be treated is allowed to flow into the inlet near the cation exchange membrane 1 on the other side for the cation exchange. The cation X ⁺ is moved to the anode 10 side while adsorbing and removing the cation X ⁺ in the body, and further moved to the anode 10 side while adsorbing and removing the anion Y ⁻ in the anion exchanger, and processed from the outlet near the anion exchange membrane 2. It may be a method of obtaining water. The filling ratio of the monolith and the ion exchange resin in the deionization chamber 15 can be arbitrarily determined depending on the properties of the water to be treated, but preferably the monolith: ion exchange resin is 1: 0.5 to 1: 10.

  The electric deionized water production apparatus of the present invention can be applied and combined in the same way as a conventional ion exchange apparatus. For example, it can be a softening apparatus using only a decation chamber or a mixed bed type ion exchange in the latter stage A vessel can be attached to further improve the quality of the treated water.

  EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.

<Production of first monolithic ion exchanger (Reference Example 1)>
(Step I; production of monolith intermediate)
19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water containing 1.8 ml of THF, and a vacuum stirring defoaming mixer which is a planetary stirring device. (EM Co., Ltd.) was used and stirred under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion. The emulsion was immediately transferred to a reaction vessel, and after sealing, it was allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with isopropanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. The average diameter of the openings (mesopores) where the macropores and macropores of the monolith intermediate were measured by mercury porosimetry was 56 μm, and the total pore volume was 7.5 ml / g.

(Manufacture of monoliths)
Next, 49.0 g of styrene, 1.0 g of divinylbenzene, 50 g of 1-decanol, and 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). Next, the monolith intermediate was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 7.6 g was collected. The separated monolith intermediate is put in a reaction vessel having an inner diameter of 90 mm, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolith-like contents having a thickness of about 30 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).

  FIG. 1 shows the result of observing the internal structure of the monolith (dry body) containing 1.3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer obtained by SEM as described above. The SEM image in FIG. 1 is an image at an arbitrary position on a cut surface obtained by cutting a monolith at an arbitrary position. As is clear from FIG. 1, the monolith has a continuous macropore structure, and the skeleton constituting the continuous macropore structure is much thicker than that of the comparative example of FIG. The thickness of the part was thick.

  Next, the thickness of the wall part and the area of the skeleton part appearing in the cross section were measured from two SEM images obtained by cutting the obtained monolith at a position different from the above position, excluding the subjectivity, and three convenient points. The wall thickness was an average of 8 points obtained from one SEM photograph, and the skeleton area was determined by image analysis. The wall portion has the above definition. Moreover, the skeleton part area was shown by the average of three SEM images. As a result, the average thickness of the wall portion was 30 μm, and the area of the skeleton portion represented by the cross section was 28% in the SEM image. Moreover, the average diameter of the opening of the monolith measured by mercury porosimetry was 31 μm, and the total pore volume was 2.2 ml / g. The results are summarized in Tables 1 and 2. In Table 1, the preparation column shows, in order from the left, the vinyl monomer used in Step II, the crosslinking agent, the monolith intermediate obtained in Step I, and the organic solvent used in Step II.

(Production of monolith cation exchanger)
The monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the monolith was 27 g. To this, 1500 ml of dichloromethane was added and heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or lower, 145 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was then washed with methanol to remove dichloromethane and further washed with pure water to obtain a monolith cation exchanger having a continuous macropore structure.

  The swelling rate before and after the reaction of the obtained cation exchanger was 1.7 times, and the ion exchange capacity per volume was 0.67 mg equivalent / ml in a water-wet state. The average diameter of the openings of the organic porous ion exchanger in the water wet state was estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water wet state, and was 54 μm, and was obtained by the same method as for the monolith. The average thickness of the wall part constituting the skeleton was 50 μm, the skeleton part area was 28% in the photographic region of the SEM photograph, and the total pore volume was 2.2 ml / g. Moreover, the ion exchange zone length regarding the sodium ion of this monolith cation exchanger was 22 mm in LV = 20 m / h. The differential pressure coefficient, which is an index of pressure loss when water is permeated, was 0.016 MPa / m · LV. The results are summarized in Table 2.

  Next, in order to confirm the distribution state of the sulfonic acid group in the monolith cation exchanger, the distribution state of sulfur atoms was observed by EPMA. The results are shown in FIGS. FIG. 2 shows a distribution state of sulfur atoms on the surface of the cation exchanger, and FIG. 3 shows a distribution state of sulfur atoms in the cross-section (thickness) direction of the cation exchanger. 2 and 3, it can be seen that the sulfonic acid groups are uniformly introduced into the surface of the cation exchanger and inside the skeleton (cross-sectional direction).

<Production of first monolith ion exchanger (Reference Examples 2 to 11)>
(Manufacture of monoliths)
Table 1 shows the amount of styrene used, the type and amount of crosslinking agent, the type and amount of organic solvent, the porous structure of the monolith intermediate coexisting during styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used. A monolith was produced in the same manner as in Reference Example 1 except for the change. The results are shown in Tables 1 and 2. In addition, from the SEM images (not shown) of Reference Examples 2 to 11 and Table 2, the average diameter of the openings of the monoliths of Reference Examples 2 to 11 is as large as 22 to 70 μm, and the average thickness of the walls constituting the skeleton is also 25 to 25 mm. It was as thick as 50 μm, and the skeletal area was 26-44% in the SEM image area, and it was a monolith of bone.

(Production of monolith cation exchanger)
The monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 1 to produce a monolith cation exchanger having a continuous macropore structure. The results are shown in Table 2. The average diameters of the openings of the monolith cation exchangers of Reference Examples 2 to 11 are 46 to 138 μm, the average thickness of the wall portion constituting the skeleton is also as thick as 45 to 110 μm, and the skeleton area is 26 to 44% in the SEM image region. The ion exchange zone length was shorter than the conventional one, and the differential pressure coefficient was also low. The exchange capacity per volume also showed a large value. The monolith cation exchanger of Reference Example 8 was also evaluated for mechanical properties.

(Mechanical property evaluation of monolith cation exchanger)
The monolith cation exchanger obtained in Reference Example 8 was cut into a strip of 4 mm × 5 mm × 10 mm in a wet state, and used as a test piece for a tensile strength test. The test piece was attached to a tensile tester, the head speed was set to 0.5 mm / min, and the test was performed at 25 ° C. in water. As a result, the tensile strength and the tensile modulus were 45 kPa and 50 kPa, respectively, which were much larger than those of the conventional monolith cation exchanger. Further, the tensile elongation at break was 25%, which was a value larger than that of the conventional monolith cation exchanger.

Reference Examples 12 and 13
(Manufacture of monoliths)
A monolith having the same composition and structure as Reference Example 4 was produced in the same manner as Reference Example 1 except that the amount of styrene used, the amount of crosslinking agent used, and the amount of organic solvent used were changed to the amounts shown in Table 1. . Reference Example 13 was carried out in the same manner as Reference Example 12 except that a reaction vessel having an inner diameter of 110 mm was used instead of the reaction vessel having an inner diameter of 75 mm. The results are shown in Tables 1 and 2.

(Production of monolith anion exchanger)
The monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. To this, 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropwise addition, the temperature was raised and reacted at 35 ° C. for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was extracted with a siphon, washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolithic organic porous material, 1000 ml of THF and 600 ml of a 30% trimethylamine aqueous solution were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with a methanol / water mixed solvent, then washed with pure water and isolated.

  Ion exchange capacity per volume of anion exchangers of Reference Example 12 and Reference Example 13, average diameter of openings of organic porous ion exchanger in water-wet state, wall portion constituting skeleton determined by the same method as monolith Table 2 summarizes the average thickness, skeleton area (ratio in the photographic region of the SEM photograph), total pore volume, ion exchange zone length, differential pressure coefficient, and the like.

  Next, in order to confirm the distribution state of the quaternary ammonium groups in the porous anion exchanger, the anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride form, and then the distribution state of chlorine atoms was observed by EPMA. As a result, it was confirmed that the chlorine atoms were uniformly distributed not only on the skeleton surface of the anion exchanger but also inside the skeleton, and the quaternary ammonium groups were uniformly introduced into the anion exchanger.

<Production of Second Monolith Ion Exchanger (Reference Example 14)>
(Step I; production of monolith intermediate)
5.4 g of styrene, 0.17 g of divinylbenzene, 1.4 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture was added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Co.) as a planetary stirring device. Was used under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion. This emulsion was quickly transferred to a reaction vessel and allowed to polymerize at 60 ° C. for 24 hours in a static state after sealing. After completion of the polymerization, the content was taken out, extracted with methanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. When the internal structure of the monolith intermediate (dry body) obtained in this way was observed with an SEM image (FIG. 7), the wall portion separating two adjacent macropores was very thin and rod-shaped, but the open cell structure The average diameter of the openings (mesopores) where the macropores overlap with each other as measured by the mercury intrusion method was 70 μm, and the total pore volume was 21.0 ml / g.

(Manufacture of monocontinuous monolith)
Subsequently, 76.0 g of styrene, 4.0 g of divinylbenzene, 120 g of 1-decanol, and 0.8 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). Next, the monolith intermediate was cut into a disk shape having a diameter of 70 mm and a thickness of about 40 mm to fractionate 4.1 g. The separated monolith intermediate is placed in a reaction vessel having an inner diameter of 75 mm, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolithic contents having a thickness of about 60 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).

  When the internal structure of the monolith (dry body) containing 3.2 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer obtained in this way was observed by SEM, the monolith had a skeleton and pores, respectively. It was a three-dimensional continuous structure with both phases intertwined. Moreover, the thickness of the skeleton measured from the SEM image was 10 μm. Further, the size of the three-dimensionally continuous pores of the monolith measured by mercury porosimetry was 17 μm, and the total pore volume was 2.9 ml / g. The results are summarized in Tables 3 and 4. In Table 4, the thickness of the skeleton was represented by the diameter of the skeleton.

(Production of co-continuous monolithic cation exchanger)
The monolith produced by the above method was cut into a disk shape having a diameter of 75 mm and a thickness of about 15 mm. The weight of the monolith was 18 g. To this was added 1500 ml of dichloromethane, heated at 35 ° C. for 1 hour, cooled to 10 ° C. or lower, gradually added 99 g of chlorosulfuric acid, heated up and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was then washed with methanol to remove dichloromethane and further washed with pure water to obtain a monolith cation exchanger having a co-continuous structure.

  A part of the obtained cation exchanger was cut out and dried, and then its internal structure was observed by SEM. As a result, it was confirmed that the monolith cation body maintained a co-continuous structure. The SEM image is shown in FIG. Moreover, the swelling ratio before and after the reaction of the cation exchanger was 1.4 times, and the ion exchange capacity per volume was 0.74 mg equivalent / ml in a water-wet state. The size of the continuous pores of the monolith in the water wet state was estimated from the value of the monolith and the swelling ratio of the cation exchanger in the water wet state to be 24 μm, the skeleton diameter was 14 μm, and the total pore volume was 2. It was 9 ml / g.

  The differential pressure coefficient, which is an index of pressure loss when water is permeated, was 0.052 MPa / m · LV. Furthermore, when the ion exchange zone length for sodium ions of the monolith cation exchanger was measured, the ion exchange zone length at LV = 20 m / h was 16 mm. Amberlite IR120B (a commercially available strong acid cation exchange resin) It was not only overwhelmingly shorter than the value (320 mm) manufactured by Rohm and Haas, but also shorter than the value of the monolithic porous cation exchanger having a conventional open cell structure. The results are summarized in Table 4.

  Next, in order to confirm the distribution state of the sulfonic acid group in the monolith cation exchanger, the distribution state of sulfur atoms was observed by EPMA. The results are shown in FIGS. 9 and 10, the left and right photographs correspond to each other. FIG. 9 shows a distribution state of sulfur atoms on the surface of the cation exchanger, and FIG. 10 shows a distribution state of sulfur atoms in the cross-section (thickness) direction of the cation exchanger. In the photograph on the left side of FIG. 9, a part extending in a horizontal direction is a skeleton part, and in the photograph on the left side of FIG. 10, two circular shapes are cross sections of the skeleton. 9 and 10, it can be seen that the sulfonic acid groups are uniformly introduced into the surface of the cation exchanger and inside the skeleton (cross-sectional direction).

<Production of Second Monolith Ion Exchanger (Reference Examples 15 to 17)>
(Manufacture of monolith with co-continuous structure)
Except for changing the amount of styrene used, the amount of crosslinking agent used, the amount of organic solvent used, the porous structure of the monolith intermediate coexisting during styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used as shown in Table 3. A monolith having a co-continuous structure was produced in the same manner as in Reference Example 14. Reference Example 17 was carried out in the same manner as Reference Example 14 except that a reaction vessel having an inner diameter of 110 mm was used instead of the reaction vessel having an inner diameter of 75 mm. The results are shown in Tables 3 and 4.

(Production of monolith cation exchanger having a co-continuous structure)
The monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 14 to produce a monolith cation exchanger having a co-continuous structure. The results are shown in Table 4. Moreover, the internal structure of the obtained monolithic cation exchanger having a co-continuous structure is as follows. The monolithic cation exchangers obtained in Reference Examples 15 to 17 from the SEM images not shown and Table 4 have conventional ion exchanger lengths. Shorter and the differential pressure coefficient showed a smaller value. Moreover, the exchange capacity per unit volume also showed a larger value than before. The monolith cation exchanger of Reference Example 15 was also evaluated for mechanical properties.

(Mechanical property evaluation of monolith cation exchanger)
The monolith cation exchanger obtained in Reference Example 15 was cut into a strip of 4 mm × 5 mm × 10 mm in a wet state of water and used as a test piece for a tensile strength test. The test piece was attached to a tensile tester, the head speed was set to 0.5 mm / min, and the test was performed at 25 ° C. in water. As a result, the tensile strength and the tensile modulus were 23 kPa and 15 kPa, respectively, which were significantly larger than the conventional monolith cation exchanger. Further, the tensile elongation at break was 50%, which was a value larger than that of the conventional monolith cation exchanger.

Reference Examples 18 and 19
(Manufacture of monolith with co-continuous structure)
Except for changing the amount of styrene used, the amount of crosslinking agent used, the amount of organic solvent used, the porous structure of the monolith intermediate coexisting during styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used as shown in Table 3. A monolith having a co-continuous structure was produced in the same manner as in Reference Example 14. Reference Example 19 was carried out in the same manner as Reference Example 18 except that a reaction vessel having an inner diameter of 110 mm was used instead of the reaction vessel having an inner diameter of 75 mm. The results are shown in Tables 3 and 4.

(Production of monolith anion exchanger having a co-open cell structure)
The monolith produced by the above method was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm. To this, 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropping, the temperature was raised and the reaction was carried out at 35 ° C. for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was extracted with a siphon, washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolithic organic porous material, 1000 ml of THF and 600 ml of a 30% trimethylamine aqueous solution were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with a methanol / water mixed solvent, then washed with pure water and isolated.

  The ion exchange capacity per volume of the anion exchangers of Reference Example 18 and Reference Example 19, the average diameter of the continuous pores of the organic porous ion exchanger in a water-wet state, and the thickness of the skeleton determined by the same method as that of the monolith Table 4 summarizes the total pore volume, ion exchange zone length, differential pressure coefficient, and the like. Moreover, the internal structure of the obtained monolith anion exchanger having a co-continuous structure was observed by an SEM image (not shown).

  Next, in order to confirm the distribution state of the quaternary ammonium groups in the monolith anion exchanger, the anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride form, and then the distribution state of chlorine atoms was observed by EPMA. As a result, it was confirmed that the chlorine atoms were uniformly distributed not only on the surface of the anion exchanger but also inside, and the quaternary ammonium groups were uniformly introduced into the anion exchanger.

Reference Example 20
(Manufacture of monolithic organic porous material having a continuous macropore structure (known product))
A monolithic organic porous body having a continuous macropore structure was produced according to the production method described in JP-A-2002-306976. That is, 19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of SMO and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Corp.) which is a planetary stirring device. Was used under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion. The emulsion was immediately transferred to a reaction vessel, and after sealing, it was allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with isopropanol, and then dried under reduced pressure to produce a monolithic organic porous body having a continuous macropore structure.

  The SEM representing the internal structure of the organic porous material containing 3.3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained had the same structure as FIG. As is clear from FIG. 12, the organic porous body has a continuous macropore structure, but the thickness of the wall part constituting the skeleton of the continuous macropore structure is thinner than that of the example, and from the SEM image The measured wall thickness average thickness was 5 μm, and the skeleton area was 10% in the SEM image area. Moreover, the average diameter of the opening of the organic porous material measured by mercury porosimetry was 29 μm, and the total pore volume was 8.6 ml / g. The results are summarized in Table 5. In Tables 1, 2 and 5, the mesopore diameter means the average diameter of the openings. Moreover, in Tables 1-5, the value of thickness, skeleton diameter, and a void | hole each shows an average.

(Production of monolithic organic porous cation exchanger having a continuous macropore structure (known product))
The organic porous body produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the organic porous material was 6 g. To this was added 1000 ml of dichloromethane, and the mixture was heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or less, 30 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was washed with methanol to remove dichloromethane and further washed with pure water to obtain a monolithic porous cation exchanger having a continuous macropore structure. The swelling ratio before and after the reaction of the obtained cation exchanger was 1.6 times, and the ion exchange capacity per volume was 0.22 mg equivalent / ml in a water-wet state, which was a small value compared to Reference Examples 1-19. Indicated. The average diameter of the mesopores of the organic porous ion exchanger in the water wet state was 46 μm as estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water wet state. The average thickness was 8 μm, the skeleton part area was 10% in the SEM image area, and the total pore volume was 8.6 ml / g. The differential pressure coefficient, which is an index of pressure loss when water is permeated, was 0.013 MPa / m · LV. The results are summarized in Table 5. The monolith cation exchanger obtained in Reference Example 20 was also evaluated for mechanical properties.

(Mechanical property evaluation of conventional monolith cation exchanger)
The monolith cation exchanger obtained in Reference Example 20 was subjected to a tensile test by the same method as the evaluation method of Reference Example 8. As a result, the tensile strength and the tensile modulus were 28 kPa and 12 kPa, respectively, which were lower than the monolith cation exchanger of Reference Example 8. The tensile elongation at break was 17%, which was smaller than that of the monolith cation exchanger of the present invention.

Reference Examples 21-23
(Manufacture of monolithic organic porous body having continuous macropore structure)
A monolithic organic porous material having a continuous macropore structure according to the conventional technique in the same manner as in Reference Example 20, except that the amount of styrene used, the amount of divinylbenzene, and the amount of SMO used are changed to the amounts shown in Table 5. The body was manufactured. The results are shown in Table 5. Further, the internal structure of the monolith of Reference Example 23 was observed with an SEM (not shown). In addition, Reference Example 23 is a condition for minimizing the total pore volume, and an opening cannot be formed by adding less water to the oil phase part. In all of the monoliths of Reference Examples 21 to 23, the opening diameter is small as 9 to 18 μm, the average thickness of the wall portion constituting the skeleton is as thin as 15 μm, and the skeleton portion area is as small as 22% at the maximum in the SEM image region. It was.

(Production of monolithic organic porous cation exchanger having a continuous macropore structure)
The organic porous material produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 20 to produce a monolithic porous cation exchanger having a continuous macropore structure. The results are shown in Table 5. If the opening diameter is increased, the thickness of the wall portion is reduced or the skeleton is reduced. On the other hand, when the wall was made thicker or the skeleton was made thicker, the diameter of the opening tended to decrease. As a result, when the differential pressure coefficient was kept low, the ion exchange capacity per volume decreased, and when the ion exchange capacity was increased, the differential pressure coefficient increased.
Reference Example 24
(Production of monolithic organic cation exchanger having a continuous macropore structure)
27.7 g of styrene, 6.9 g of divinylbenzene, 0.14 g of azobisisobutyronitrile (ABIBN) and 3.8 g of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 450 ml of pure water and stirred for 2 minutes at 20,000 rpm with a homogenizer, and a water-in-oil emulsion. Got. After emulsification, the water-in-oil emulsion was transferred to a stainless steel autoclave, sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with Soxhlet for 18 hours with isopropanol, unreacted monomer and sorbitan monooleate were removed, and dried under reduced pressure at 40 ° C. overnight. After separating 11.5 g of an organic porous material containing 14 mol% of a crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained, 800 ml of dichloroethane was added, and the mixture was heated at 60 ° C. for 30 minutes. After cooling to room temperature, 59.1 g of chlorosulfuric acid was gradually added and reacted at room temperature for 24 hours. Thereafter, acetic acid was added, the reaction product was poured into a large amount of water, washed with water and dried to obtain a porous cation exchanger. The ion exchange capacity of this porous body is 4.4 mg equivalent / g in terms of dry porous body and 0.32 mg equivalent / ml in terms of wet volume. By mapping sulfur atoms using EPMA, sulfonic acid groups It was confirmed that was uniformly introduced into the porous body. Further, as a result of SEM observation, the internal structure of this organic porous body has an open cell structure, most of the macropores having an average diameter of 30 μm overlap, and the pore diameter of the mesopore formed by the overlap of the macropores and the macropores is 5 μm. The total pore volume was 10.1 ml / g, and the BET specific surface area was 10 m ² / g.

  In addition, about the monolith ion exchanger manufactured by Reference Examples 1-11 and Reference Examples 20-23, the relationship between a differential pressure coefficient and the ion exchange capacity per volume was shown in FIG. As is clear from FIG. 4, it can be seen that the known reference examples 20 to 23 have a poor balance between the differential pressure coefficient and the ion exchange capacity with respect to the reference examples 1 to 11. On the other hand, it can be seen that Reference Examples 1 to 11 have a large ion exchange capacity per volume and a low differential pressure coefficient.

Reference Example 25
Monolith production was attempted in the same manner as in Reference Example 1 except that the type of organic solvent used in Step II was changed to dioxane, which is a good solvent for polystyrene. However, the isolated product was transparent, suggesting collapse / disappearance of the porous structure. SEM observation was performed for confirmation, but only a dense structure was observed, and the continuous macropore structure disappeared.

(Production of electric decation water production equipment)
An electric deionized water production apparatus having the following specifications as shown in the simplified diagram of FIG. 17 was used.
-Cell size: 160 ml (5 cm long x 4 cm wide x height (length between electrodes) 8 cm)
・ Cell container; internal volume 160ml
Anion exchange resin (filled on the anode side); 120 ml (IRA402BL), length 5 cm × width 4 cm × height 6 cm,
Cationic monolith: 5 cm long × 4 cm wide × 2 cm high obtained by cutting the monolith ion exchanger of Reference Example 8 in a wet state;
・ Treated water: Reverse osmosis membrane permeate, conductivity of about 20 μS / cm, flow rate of 15 l / hour ・ Electrode water: both anode water and cathode water, flow rate of 5 l / hour

(Operation of electric deionized water production equipment)
When the water to be treated was continuously passed through the obtained electric deionized water production apparatus at a flow rate of 15 l / hour (LV = 7.5, SV = 94 (whole)) and a direct current of 0.33 A was applied, The operating voltage was 58 V, and treated water having an electric conductivity of 0.2 μS / cm was obtained, and it was shown that pure water with high purity was produced by the electric deionized water production apparatus of the present invention. Moreover, the water flow differential pressure was 4.7 kPa. Moreover, when the inside of the container was observed during continuous operation, the anion exchange resin expanded and the cation monolith was crushed, and the mixed ion exchanger was in close contact with the container.

(Production of electric decation water production equipment)
An electric decationized water production apparatus was produced and operated in the same manner as in Example 1 except that the monolith ion exchanger of Reference Example 17 was used instead of the monolith ion exchanger of Reference Example 8. . As in Example 1, the water to be treated was continuously passed through the electric deionized water production apparatus at a flow rate of 15 l / hour, and a direct current of 0.33 A was applied. A treated water of 0.2 μS / cm was obtained, and it was shown that pure water with high purity was produced by the electric deionized water production apparatus of the present invention. The water differential pressure was 3.0 kPa.

Comparative Example 1
(Production of electric decation water production equipment)
In place of the monolith ion exchanger of Reference Example 8, the monolith ion exchanger of Reference Example 24 was used, and an electric decationized water production apparatus was produced and operated in the same manner as in Example 1. . As in Example 1, the water to be treated was continuously passed through the electric deionized water production apparatus at a flow rate of 15 l / hour and a direct current of 0.33 A was applied. The operating voltage was 64 V, and the conductivity A treated water of 0.8 μS / cm was obtained. The water flow differential pressure was 67 kPa.

  The electric deionized water production apparatus of the present invention is used in various industries such as semiconductor manufacturing industry, pharmaceutical industry, food industry, power plant, laboratory, etc. using deionized water, or production of sugar solution, juice, wine, etc. Is done.

DESCRIPTION OF SYMBOLS 1 Cation exchange membrane 2 Anion exchange membrane 3a-3c Inlet 4a-4c Outlet 5a, 5b Communication pipe 6 Decation chamber 7 Deanion chamber 8 Nonconductor spacer 9 Cathode 10 Anode 11 Anion exchange resin 12 Cation exchange Resin 13 Cationic monolith 14 Anion monolith 15 Deionization chamber 61 Skeletal phase 62 Pore phase

Claims (9)

  A DC electric field is applied to the deionization chamber filled with the ion exchanger so that the excluded ions migrate in the same direction or in the opposite direction to the direction of water flow in the ion exchanger. In an electric deionized water production apparatus for removing adsorbed ionic impurities out of the system, the ion exchanger is a mixture of a monolithic organic porous ion exchanger and a granular ion exchange resin, and the monolithic organic The porous ion exchanger is a continuous macropore structure in which bubble-like macropores overlap each other, and the overlapping portion is an opening having an average diameter of 30 to 300 μm in a wet state of water, and the total pore volume is 0.5 to 5 ml / g. The ion exchange capacity per volume in a wet state of water is 0.4 to 5 mg equivalent / ml, the ion exchange groups are uniformly distributed in the porous ion exchanger, and In the cut surface of the SEM images of the structure (dried body), skeletal portion area appearing in cross section, electrodeionization water producing apparatus, characterized in that from 25 to 50% in image area.   A DC electric field is applied to the deionization chamber filled with the ion exchanger so that the ions to be excluded migrate in the same direction or the reverse direction with respect to the direction of water flow in the ion exchanger. In an electric deionized water production apparatus for removing adsorbed ionic impurities out of the system, the ion exchanger is a mixture of a monolithic organic porous ion exchanger and a granular ion exchange resin, and the monolithic organic The porous ion exchanger is a three-dimensional one having a thickness of 1 to 60 μm made of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit among all the structural units into which ion exchange groups are introduced. A continuous structure having three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, and the total pore volume is 0.5 to 5 ml / g, Per volume in wet condition Ion exchange capacity 0.3~5mg was equivalent / ml, it electrodeionization water producing apparatus according to claim ion exchange group is uniformly distributed in the porous ion exchanger. A deanion chamber partitioned by an anion exchange membrane on one side and an ion exchange membrane on the other side, an anode disposed outside the anion exchange membrane on the one side, and an outer side of the ion exchange membrane on the other side And supplying water to be treated from the vicinity of the anion exchange membrane on one side in the deanion chamber, and from the vicinity of the ion exchange membrane on the other side in the deanion chamber. An anion cell for obtaining treated water;
A decation chamber partitioned by a cation exchange membrane on one side and an ion exchange membrane on the other side; a cathode disposed outside the cation exchange membrane on the one side; and an outer side of the ion exchange membrane on the other side The first treated water of the anion cell is supplied from the vicinity of one cation exchange membrane in the decation chamber, and the other ion exchange in the decation chamber is provided. The apparatus for producing electrical deionized water according to claim 1 or 2, further comprising a cation cell for obtaining the second treated water from the vicinity of the membrane. A decation chamber partitioned by a cation exchange membrane on one side and an ion exchange membrane on the other side; a cathode disposed outside the cation exchange membrane on the one side; and an outer side of the ion exchange membrane on the other side The first treatment is performed from the vicinity of the cation exchange membrane on the one side in the decation chamber by supplying water to be treated from the vicinity of the cation exchange membrane on the other side in the decation chamber. A cation cell for obtaining water;
A deanion chamber partitioned by an anion exchange membrane on one side and an ion exchange membrane on the other side, an anode disposed outside the anion exchange membrane on the one side, and an outer side of the ion exchange membrane on the other side The first treated water of the cation cell is supplied from the vicinity of the anion exchange membrane on one side in the deanion ion chamber, and the ion exchange on the other side in the deanion ion chamber is provided. The electric deionized water production apparatus according to claim 1 or 2, further comprising an anion cell for obtaining the second treated water from the vicinity of the membrane.   The ion exchanger filled on the cathode side of the cation cell is a monolithic organic porous cation exchanger, or the ion exchanger filled on the anode side is a monolithic organic porous anion exchanger. The ion exchanger filled on the anode side of the anion cell is a monolithic organic porous anion exchanger, or the ion exchanger filled on the cathode side is a monolithic organic porous cation exchange The apparatus for producing electrical deionized water according to claim 3 or 4, wherein the apparatus is a body.   An intermediate ion exchange membrane is provided between the anion exchange membrane on one side and the cation exchange membrane on the other side, and a deionization chamber partitioned by the one side anion exchange membrane and the intermediate ion exchange membrane, A decation chamber is defined by the cation exchange membrane on the other side and the intermediate ion exchange membrane, an anode outside the one side anion exchange membrane, and a cathode outside the cation exchange membrane on the other side The deionization cell is configured to supply water to be treated from the vicinity of the other cation exchange membrane in the decation chamber, and from the vicinity of the intermediate ion exchange membrane in the decation chamber. Treated water is obtained, the first treated water is supplied from the vicinity of one anion exchange membrane in the deanion chamber, and the second treated water is obtained from the vicinity of the intermediate ion exchange membrane in the deanion chamber. The electric deionized water production apparatus according to claim 1 or 2.   An intermediate ion exchange membrane between a cation exchange membrane on one side and an anion exchange membrane on the other side, and a decation chamber partitioned by the one side cation exchange membrane and the intermediate ion exchange membrane; A deanion chamber defined by the anion exchange membrane on the other side and the intermediate ion exchange membrane is configured, and a cathode is provided outside the cation exchange membrane on the one side, and an anode is provided outside the anion exchange membrane on the other side. The deionization cell is configured to supply water to be treated from the vicinity of the anion exchange membrane on the other side in the deanion chamber, and from the vicinity of the intermediate ion exchange membrane in the deanion chamber. Treated water is obtained, the first treated water is supplied from the vicinity of one cation exchange membrane in the decation chamber, and the second treated water is obtained from the vicinity of the intermediate ion exchange membrane in the decation chamber. The electric deionized water production apparatus according to claim 1 or 2.   The ion exchanger filled on the cathode side of the decation chamber is a monolithic organic porous cation exchanger, or the ion exchanger filled on the anode side of the deion chamber is a monolith. It is an organic porous anion exchanger, The electric deionized water manufacturing apparatus of Claim 6 or 7 characterized by the above-mentioned.   A deionization chamber partitioned by an anion exchange membrane on one side and a cation exchange membrane on the other side, an anode disposed outside the anion exchange membrane on one side, and a cation exchange membrane on the other side It has a cathode arranged on the outside, and the monolithic organic porous anion exchanger is filled on the anode side of the deionization chamber, or the monolithic organic porous cation exchanger on the cathode side of the deionization chamber In a deionization cell filled with water, whether water to be treated is supplied from the vicinity of one anion exchange membrane in the deionization chamber to obtain treated water from the vicinity of the other cation exchange membrane in the deionization chamber. Or the water to be treated is supplied from the vicinity of the other cation exchange membrane in the deionization chamber to obtain treated water from the vicinity of the anion exchange membrane on one side in the deionization chamber. Item 3. The electric deionized water production apparatus according to Item 1 or 2.